Beta-amino carbonyl catalysts for polyurethane preparation

ABSTRACT

Provided as catalysts for the formation of cellular urethane polymers ranging from flexible to rigid foams, are beta-amino carbonyl compounds wherein carbonyl is present as an amido or carboxylic acid ester group and the beta-amino group is present as dialkylamino or an N-morpholino or N,N&#39;&#39;-piperazino heterocyclic nucleus. Effective in the catalysis of the waterisocyanate reaction, these beta-amino amides and beta-amino esters are used with particular advantage in the manufacture of water-blown flexible foams, both molded and free-rise, including high-resilience and flame-retarded foam. The beta-amino carbonyl catalysts allow for the formation of foam products essentially free of the odor associated with amines such as Nethylmorpholine. In view of this highly desirable characteristic and their other beneficial properties, the catalysts of the invention are advantageously employed as direct replacements for N-ethylmorpholine in high-resilience and other foam formulations.

United States Patent 1191 Priest et al.

. [45] June 28, 1974 BETA-AMINO CARBONYL CATALYSTS FOR POLYURETHANEPREPARATION [73] Assignee: Union Carbide Corporation, New

York, N.Y.

[22] Filed: Nov; 27, 1972 [21] Appl. No.: 309,906

[5 2] US. C1,: ..260/2.5 AC, 260/75 NC,-

260/77.5 AC [51] Int. Cl C08g 22/38, C08g 22/34 [58] Field of Search...260/2.5 AC, 77.5 AC, 75 NC [56] References Cited UNITED STATES PATENTS2,866,762 12/1958 Brochagen 260/2.5 AC 2,913,425 11/1959 Muller...260/2.5 AC 3,019,200 1/1962 Gee... 260/2.5 AC 3,073,787 1/1963 Krakler260/77.5 AC 3,168,497 2/1965 Twitchett 260/77.5 AC 3,234,153 2/1966Britain 260/77.5-AC 3,313,744 4/1967 Rice 260/2.5 AC

FOREIGN PATENTS OR APPLlCATlONS 852,138 10/1960 Great Britain 260/2.5 AC2/1963 Australia 260/77.5 AC

6/1960 Great Britain 260/2.5 AC

839,186 1,027,870 4/1958 Germany 260/2.5 AC 924,895 5/1963 Great Britain260/2.5 AC

Primary Examiner-Donald E. Czaja Assistant Examiner-C. Warren IvyAttorney, Agent, or Firm-Marylin Klosty 5 7] ABSTRACT Provided ascatalysts for the formation of cellular urethane polymers ranging fromflexible to rigid foams, are beta-amino carbonyl compounds whereincarbonyl is present as an amido or carboxylic acid ester group .and thebeta-amino group is present as dialkylamino catalysts allow for theformation of foam products essentially free of the odor associated withamines such as N-ethylmorpholine. In view of this highly desirablecharacteristic and their other beneficial properties, the catalysts ofthe invention are advantageously employed as direct replacements for'N-ethylmorpholine in high-resilience and other foam formulations.

40 Claims, No-Drawings BETA-AMINO CARBONYL CATALYSTS FOR POLYURETHANEPREPARATION BACKGROUND OF THE INVENTION This invention pertains toparticular beta-amino carbonyl compounds as catalysts for the formationof urethane polymers by the reaction of organic isocyanates with activehydrogen-containing compounds.

It is well known to the art that urethane polymers are generally ashigh-resiliencefoams. In view of the aforeprovided by the reaction oforganic polyisocyanates and active hydrogen-containing organiccompounds, usually inthe presence of one .or more activators, and thatblowing action is provided when cellular products including flexible,semi-flexible and rigid foams, are desired. It is also known that anumber of different chemical reactions occur during polymer formationand expansion. For example, in addition to the chainextending,urethane-forming reaction between free isowater, thereby generatingcarbon dioxide blowing agent in situ, and introducing furthercross-links comprising urea groups. The nature of the cellular structureand the physical and mechanical properties of the'foam are influenced bythe extent of such reactions, and the relative. rates and point in timeat which they occur. Al-

though balancing these variables so as to achieve a particular type orgrade of foam can be controlled to some extent by the functionality,molecular weight and other structural features of the polyisocyanate andactive hydrogen-containing reactants, the catalyst system also plays asignificant role in this respect.

Among the relatively few compounds that have achieved widespreadcommercial application as catalysts in polyurethane manufacture are:tertiary amines consisting of carbon, hydrogen and nitrogen, astypically illustrated by l,4-diazabicyclo[2.2.2loctane(triethylenediamine) and -N,N,N,N'-tetramethyl-l,3- butanediamine; andtertiary amines consisting .of carbon, hydrogen, nitrogen and oxygenwherein oxygen is present as ether oxygen, as typically illustrated bybis[- 2-(N,N-dimethylamino)ethyl]ether and N- ethylmorpholine. Withparticular reference to the manufacture of flexible polyetherpolyol-based urethane foams, such tertiary amines are usually employedin combination with auxiliary catalysts comprising organic derivativesof tin such as stannous Octoate and bibutyltin dilaurate, in order toprovide a synergistic activation of the chain-extending reaction.

A relatively recent advance in the area of flexible polyurethane foamtechnology which has triggered intensive research effort to developimproved activators, is the advent of reaction mixtures having asufficiently high reactivity to provide more complete reactions duringpolymer formation and expansion, thereby eliminating the need incommercial practice to post-cure the foam at high temperatures(300500F.) to obtain a product of satisfactory overall properties. Inaddition to the saving in cost which elimination of high temperaturepost-curing offers to the foam manufacturer, such highly reactiveformulations also provide flexible foams of generally improvedflammability characteristics,

said combination of properties, high-resilience foam is particularlysuited as cushioning material in automotive interiors. In the productionof at least a substantial proportion of high-resilience foam beingmanufactured at the present time, the aforementioned N- ethylmorpholineis used as a major component of mixed catalyst systems. However, theusefulness of N- ethylmorpholine in the manufacture of high-resiliencefoam as well as other types of cellular urethanes, is attended withcertain disadvantages. Thus, N-

ethylmorpholine suffersthe 'very serious drawback of having aparticularly strong amine odor. The large. quantities ofN-ethylmorpholine which are employed relative to other catalystcomponents of the foam formulation, causes an obnoxious atmosphere atand surrounding the foam manufacturing plant site and also providesfoams having a strong residual amine odor. This compound is alsoassociated with a number of serious toxid effects; see, for example,Plastics Technology, Catalysts Improve As Their Need Increases pages4749 (July 1972). Consequently, it is desirable and is apr'imaryobjective of this invention to find a direct replacement forN-ethylmorpholine in the production of high-resilience foamin particularand cellular urethane manufacture generally and thereby allow for atleast a substantial reduction in the-relatively large amounts presentlyemployed. Various other objects and advantages of the present inventionwill become apparent from the accompanying'description and disclosure.

SUMMARY OFTHE INVENTION In accordance with the teachings of the presentinvention, ,cellular polyurethanes are provided by effecting reaction ofactive hydrogen-containing compounds and polyisocyanates in the presenceof a particular class of beta-amino carbonyl compounds as catalyticcomponents of the urethane-forming.reaction mixture. The catalystsemployed in the practice of this invention consist of carbon-bondednitrogen, oxygen and hydrogen atoms and contain at least one tertiarynitrogen atoms. Except for carbonyl oxygen, the remaining atoms arejoined through single bonds and thus the catalysts employed in thepractice of this invention are au ht.

group and may be the same as or different from one another; and

. Q is a member of the group consisting of an alkoxy group (-OR havingfrom one to eight carbon atoms, an N,N-dialkylamino group, N(R )(R whereR and R each represents a lower alkyl group, or a 2-(N,N-dialkylamino)ethoxy group, OCH CH N(R )(R where R and R also representlower alkyl radicals.

It is to be understood that the expression lower alkyl as used hereinincluding the claims, denotes an alkyl radical having from one to fourcarbon atoms including linear and branched radicals (that is, radicalsof the series, C,,,H wherein m is an integer from oneto four and p isone).

It has been discovered that the above-described betaamino carbonylcompounds are useful as catalytic components in the manufacture of awide variety of cellular urethanes including products ranging fromflexible to rigid foams. They are effective activators when used as thesole nitrogen-bearing catalytic component of foam formulations, althoughtheir employment in combination with other tertiary amines is within thescope of the present invention. Especially effective in the catalysis ofthe water-isocyanate reaction, these beta-amino amides and esters areused withparticular advantage in the manufacture of water-blown flexiblefoams, both molded and free-rise, including high-resilience foam. Inaddition to their versatility in this respect, they have the furtherhighly desirable characteristic of low residual odor and thus allow forthe formation of foam products essentially free of the post-cure doorassociated with N-ethylmorpholine. Other beneficial properties includeexcellent mold-release characteristics, wide formulatinglatitude withrespect to concentration of tin cocatalysts, and ability to provideopen-cell, porous foam from formulations containing an addedflame-retarding agent.

It is noted that, as a class, beta-amino amides and esters includingspecific compounds employed in the practice of this invention arereported in the literature. As far as is known, however, their abilityto function as catalysts in cellular urethane polymer formation has notbeen previously reported. On the other hand, certain of the beta-aminocarbonyl compounds employed as catalysts in the practice of thisinvention are novel compositions. These include: (1 the heterocyclicbetaamino amides encompassed by Formula I, that is, those compounds inwhich q is one and Q is an N,N- dialkylamino group; (2)3-dialkylamino-N,N- dialkylamides wherein the alkyl groups bonded toamino nitrogen are different from those bonded to amido nitrogen; and(3) 3-dialkylamino-3-alkyl-N,N- dialkylamides wherein the various alkylgroups may be the same as or different from one another.

The present invention also relates to particular blends of thebeta-amino carbonyl catalysts encompassed by Formula I with othertertiary amines, the use of such blends as mixed amine catalyst systemsfor cel lular polyurethane formation, and to the cellular urethanepolymers produced in the presence of the catalysts described herein.

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS A. TheBeta-Amino Carbonyl Catalysts In generic Formula I, the sum p-l-q is oneand thus when q is zero, p must have a value of one. In the latterevent, each C,,,l-I group shown in Formula I is a lower alkyl radical,designated herein as Rh and R and the indicated valence of carbon whichwould otherwise be in association with Y is satisfied by the additionalhydrogen atom present when p is one. The resulting saturated, acyclicbeta-amino esters and amides have the more specific Formula II:

-CHCH-CI!Q Fail-.-

.. V When Q is an alkoxy group, the catalysts encompassed by FormulaIlare alkyl beta-(dialkylamino)carboxyl t e havin he f o n F m a "1AN-oH-cH-c'i-oR1 When Q of Formula II is a 2-(N,N-dialkylamino)ethoxygroup, the catalysts are 2-(N,N-dialkylamino)ethyl 3-(N,N-dialkylamino)carboxylates having the following For u a 1 .1 32.

u NCH-CHC0CHzCH:N v 3 .7 ..-.-.Ma---V, ..a-. E9 R TE? Further, when Q isan N,N-dialkylamino group, thecatalysts encompassed by Formula II, arebeta- (dialkylamino)-N,N-dialkylamides and have the strucureshwaluths fl sw ns o mu a -C.=

CHr-CEIA (H) N-cH-pH-corn-oa, R3 R4 wherein the -C(O)Q group may bepresent as the ester groups shown in Formulas [LA and "-8 or the amidogroup shown in Formula IIC. For example, when the Q radical of FormulasIII and IV is a dialkylamino group, the respective compounds aremorpholino)-N,N'-dialkylamides and N,N'-

S piperazino-bis[3-(N"',N"-dialkylamides)]. These heterocyclicbeta-amino amide catalysts are novel compounds and have the followingmore specific Formulas III-A and lV-A, respectively;

CHa-CHz Rs In the above formulas and as shown elsewhere in the presentspecification, R R R and R represent lower alkyl radicals, R and R maybe hydrogen or lower alkyl, and R represents an alkyl radical havingfrom one to eight carbon atoms including linear and branched radicalsand is more usually lower alkyl. It is to be understood that the loweralkyls represented by R,, R ,"R

, and R and encompassed by R R and R may be the 7 .same as or differentfrom one another. The generally those represented by R and R the.resulting unsymmetrically N-substituted 3-dialkylamino-N,N-dialkylamides are new compositions including those wherein R and R arehydrogen or alkyl, as previously defined. Also novel are the3-dialkylamino-3-alkyl- N,N-dialkylamides, that-is, those compoundsencompassed by Formula ll-C in which R;, is limited to an alkyl. groupand R R R R and R are as previously 6 ethyl3-(N-methyl-N-ethylamino)propionate; and methyl3-butyl-3-(N,N-dimethylamino)heptanoate. Formula Il-B:

2-(N,N-dimethylamino)ethyl 3-(N',N-dimethylamino)propionate;

2-(N,N-diethylamino)ethyl 3-(N,N-diethylamino)- propionate;2-(N,N-diethylamin0)ethyl 3-(N,N-dimethylamino)- propionate;

2-(N,N-dimethylamino)ethyl 2-methyl-3-(N,N-dimethylamino)propionate;

' 2-(N-methyl-N-ethylamino)ethyl 3-(N',N'-dimethylamino)propionate; and2-(N,N-diethylamino)ethyl As between the various types of compoundsemployed in the practice of this invention, the catalysts encompassed byFormulas II and III are generally preferred' in that they also offer theprocessing advantage of being normally liquid materials, whereas thepiperazine derived catalysts (Formula IV) are solids. From thisstandpoint, the acyclic catalysts having Formula ll are especiallypreferred in that they are generally less viscous than the morpholinederivatives and thus can be handled and pumped more readily withoutdilution.

Typical examples of suitable catalysts for use in the formation ofcellular urethane polymers in accordance with the teachings of thisinvention are the following compounds which, for clarity, are groupedaccording to the structural formulas within which they specificallyfall, all such catalysts being within the scope of generic Formula I.

Formula lI-Az,

3-(N"-methyl-N- ethylamino)butyrate. Formula lI-C:3-dimethylamino-N,N-dimethylpropionamide;3-diethylamino-N,N-dimethylpropionamide;3-diethylamino-N,N-diethylpropionamide;3dimethylamino-N,N-di-n-propylpropionamide;3-diethylamino-N,N-di-s-butylpropionamide;-3-(N-methyl-N-ethylamino)-N'-n-butyl-N'- methylpropionamide;3-dimethylamino-2-methyl-N,N-dimethylpropionamide;3-dimethylamino-N,N-dimethylbutyramide; 3dimethylamino-N,N-dimethylpentamide; and3-diethylamino-N,N-dimethylhexamide.

Formula Ill including Formula Ill-A:

methyl 3-(N-morpholino)propi0nate;

ethyl 3-(-N-morpholino)propionate;

ethyl 2-methyl-3-(N-morpholino)propionate;

methyl '3-( N-morph olino)butyrate; 2-(N,N-dimethylamino)ethyl3-(N-morpholino)propionate; 3-(N-morpholino)-N',N'-dimethylpropionamide;3-(N-morpholino)-2-methyl-N',N'-dimethylpropionamide; and

3-(N-morpholino)-N',N'-dimethylbutyramide. Formula IV including FormulaIV-A:

dimethyl 3-(N,N-piperazino)dipropionate;

diethyl 3-(N,N-piperazino)dipropionate; di-2-(N,N-dimethylamino)ethyl'3-(N,N"-piperazino)- dipropionate; and

N,N'-piperazino-bis[ 3-( N N' '-dimethylpropionamide)].

The above-described beta-amino carbonyl compounds employed as catalystsin accordance with the present invention are readily prepared by anumber of different types of reactions. A particularly facile meth odcomprises the reaction of (A) secondary amines and (B) esteror amidoderivatives of alpha,betaunsaturated carboxylic acids. With specificreference to Formula I, the overall reaction by which such compounds areprovided is as follows:

CmHZm-Hz (Y N-H oH=o( l- Compounds of Formula I CmHau+ a I114 Reaetant AReactant B (1) compassed by Formula I, Reactant B may be: an alkyl (R ora 2-(N,N-dialkyla'mino)ethyl CH CH N(R )(R ester derivative of analpha,betaunsaturated carboxylic acid having the formula, -CH(R )=C(R)C(O)OH; or an alpha,beta-unsaturated N,N-di(lower)alkylamide having theformula, CH(R )=C(R )C(O)N(R )(R Typical examples of suitableunsaturated esters included within the definition of Reactant B are:methyl, ethyl, N-propyl, n-butyl, i-butyl, 2-ethylhexyl,2-(N,N-dimethylamino)ethyl, 2- (N ,N-diethylamino)ethyl andZ-(N-methyl-N- ethylamino)ethyl ester derivatives of acrylic,methacrylic, crotonic, Z-methylcrotonic (tiglic), 2- ethylpropenoic,2-pentenoic, 2-ethyl-2-pentenoic, 2- hexenoic and Z-heptenoic acids.Illustrative of suitable unsaturated amide reactants encompassed by thedefinition of Reactant B are the corresponding amides containingthe CH(R)=C(R.,)C(O)-nucleus of the aforesaid acids such asN,N-dimethylacrylamide, N,N-

N-methyl-N-ethylacrylamide,

diethylacrylamide, N,N-dimethylmethacrylamide, and dimethylcrotonamide.

Encompassed by the overall reaction of equation (1) is the direct l:laddition of the reactive group (or groups as in piperazine) of ReactantA across the double bond of Reactant B to form the corlustrated by thefollowing equations (2)-(6):

as well as those of equation (6) being encompassed by Formula IV.Likewise, reaction of l,4-piperazine with the alpha,beta-unsaturatedamides shown in equation (4) provides the correspondingN,N'-piperazinobis[3(-N",N"-dialkylamides)] which are also encompassedby Formula IV and defined specifically by Formula lV-A.

The addition reactions illustrated by equations(- 2)(6) are effected attemperatures within the range from about minus 15C. to about 120C. andproceed at satisfactory rates at ambient or substantially atmosphericpressures. Reactions based on dimethylamine are generally more highlyexothermic than those based on higher homologues and thus are usuallyeffected at the lower temperatures within the aforesaid range. Asrequired, temperature control is achieved in conventional manner such asby cooling or appropriate adjustment of the rate at which the reactantsare fed to the reactor. The relative proportions of reactants are suchto at least satisfy the indicated stoichiometric requirements of theaddition, although either reactant may be employed in excess ofstoichiometry to favor completion of the reactions. Usually, no morethan a l25 per cent molar excess of either reactant is employed,

As illustrated by the reaction of equation (4), the beta-amino amidecatalysts can be prepared by the addition of secondary amines toalpha,beta-unsaturated, N,Ndialkylamides. These catalysts can also beprovided by the following application of the overall reac- 9 9 quat qn)2 It is to be understood that replacement of the ester reactant shownin equation (5) with the unsaturated ester reactant shown in equation(3), provides the corresponding 2-(N,N-dialkylamino)ethyl3-(N'-morpholino)-carboxylates, such compounds, as well as the esterproducts of equation (5), being encompassed by Formula Ill. It also isto be understood that when morpholine is reacted with the unsaturatedamide reactants shown in equation (4), the products are thecorresponding 3-(N-morpholino)-N',N-dialkylamides which are alsoencompassed by Formula Ill and defined specifically by Formula III-A.Similarly, when the ester reactant shown in equation (6) is replacedwith the unsaturated ester reactant shown in equation (3), thecorresponding di-2-(N,N-dialkylamino)ethyl 3-(N',N"-piperazino)dicarboxylates are provided, such products Compounds ofFormula II, A. (2)

Compounds of Formula II, B (3) Compounds of Formula II, C (4) O (6)N-(IJH(IJH CO R1 Equation 7 R, R, R; R,

This reaction may be viewed as an extension of the addition reaction ofequation (2) in that it proceeds through intermediate formation of thealkyl beta- 65 (dialkylarnino)carboxylates (Formula Il-A) followed 9verity conditionsare employed when it is desired to recover theamid'ated product. Generally, the amidation reactions encompassed byequation (7) are effected at temperatures within the range from about100C. to

' about 250C. and at elevated pressures from about 50 to about 1,200p.s.i.g. In order to favor completion of the reaction, the aminereactant is preferably employed in excess of stoichiometry, amounts upto about a 100 per cent molar excess usually being suitable for thispurpose. The reaction of equation (7) may be carried out in batchwisefashion by initially charging total reactants to the reactor andapplying the aforesaid high temperature-elevated pressure conditions..Alternatively, the reaction may be carried out as an essentially Inaccordance with the latter two-stage process. method, a portion of totalamine reactant is fed to the unsaturated ester under the less severeaddition reaction conditions to form the 1:1 adduct, followed byreaction of the intermediate with the remainder of amine under theaforesaid more severe amidation conditions. his to be understood thatthe amine fed to the first stage may be different'from that fed to thesecond stage, thereby providing amino and amido groups hav-- ing adifferent combination of R, and R groups, that the alkyl groupsrepresented by R, and R are different from the alkyls represented by Rand B In order to minimize formation of by-products by retro-additionreactions and hydrolysis of ester reactants as well as ester products,it'is recommended practice to effect the above-described reactions underanhydrous or substantially anhydrous conditions. Thus, the reactionmedia should contain less than about 5 weight per cent water, expressedon the basis of amine reactant. Formation of by-products such asalpha,betaunsaturated amides may also be formed during the reactions.Minor amounts of compounds which have an inhibiting effect onpolymerization of such by-products may be added to the reaction media.Illustrative of suitable inhibitors are phenothiazine, p methoxyphenoland hydroquinone. The reaction media may also contain solvents ordiluents such as, for example, ethanoL,

ing after removal of more volatile components. Recovery as residueproducts is usual practice in the case of the higher molecular weightcompounds such as the morpholine-derived compounds and acyclic compoundsin which the various alkyl groups are propyl and butyl. Thepiperazine-derived catalysts are recovered by conventional liquid-solidseparation techniques. I

The effectiveness of the beta-amino carbonyl com-.

pounds as catalysts for cellular urethane manufacture as describedherein, does notdepend on their use in a rigorously pure state; Includedwithin the scope of the present invention, therefore, is the use of thecatalysts as either substantially pure compounds, in combination withone another, or in associated with impurities which may form duringtheir manufacture.

B. THE FOAM FORMULATIONS In producing cellular urethane polymers inaccordance with the teachings of this invention, the reaction mixture orfoam formulation contains, in addition to the beta-amino carbonylcatalysts, an organic polyisocyanate and an active hydrogen-containingorganic compound having an average of at least two and usually not morethan eight active hydrogen atoms present as hydroxyl groups. Suchorganic polyol reactants include compounds consisting of carbon,hydrogen and oxygen .as well as compounds which contain these elementsin combination with phosphorus, halogen, and/or nitrogen. Suitableclasses of organic polyol reactants for use bone of the aforesaidpolyols in the presence of a free radical initiator.

It is'wellknown to the polyurethane art that the particular polyolreactant or combination of polyols employed depends upon the end-use ofthe polyurethane product which in turn determines whether the product isto be provided as a flexible, semi-flexible or rigid material. For thispurpose, the polyol reactant is usually characterized by itshydroxylnumber which is determined by-and defined as the number of milligrams ofpotassium hydroxide required for the complete-neutralization of thehydrolysis product of the fully acetylated derivative prepared from 1gram of polyol or mixture of polyols. The hydroxyl number is alsodefined by the following equation which reflects its relationship withthe functionality and molecular weight of the polyol reactant...

OH =56.l X1000 Xf/M. W.

wherein OH hydroxyl number of the polyol;

f average functionality, that is, average number of hydroxyl groups permolecule of polyol; and

M. W. average molecular weight of the polyol. The beta-amino carbonylcompounds described herein are suitably employed as catalytic componentsof foam formulations containing polyols having hydroxyl numbers fromabout 20 to about 1,000. In producing flexible foams, polyols havingrelatively low hydroxyl numbers such as from about 20to about 100 aregenerally tional groups other than hydroxyl. For convenience,

this class of polyether polyols are referred to herein as Polyol I.These compounds include alkylene oxide adducts of water such aspolyethylene glycols having average molecular weights from about 200 toabout 600,

polypropylene glycols having average molecular weights from about 400 toabout 2,000, and, polyoxyalkylene polyols having a combination ofdifferent alkylene oxide units. Other suitable polyols encompassedwithin the definition of Polyol l are the. alkylene oxide adducts ofpolyhydric organic initiators, the nature of which determines theaverage hydroxyl functionality of the polyoxyalkylated product.Illustrative of suitable polyhydric organic initiators are the followingwhich can be employed individually or incombination with one another:(1) diols such as ethylene glycol, diethyl- 3-(2-hydroxyethoxy)- and3-(2-hydroxypropoxy)-l,2-

propanediols, 2,4-dimethy1-2-(2- hydroxyethoxy)methyl-pentanediol-1,5,1,1,1-tris[(2- hydroxyethoxy)methyl]ethane and 1,1,1-tris[(2-hydroxypropoxy)methy1]propane; (3) tetrols such as pentaerythritol; (4)pentols, hexols, heptanols and octanols such as glucose, sorbitol,bis(2,2,2- trimethylo1)ethy1 ether, alpha-methyl glucoside, surcrose,mannose and galactose; (5) compounds in which hydroxyl groups are bondedto an aromatic nucleus such as resorcinol, pyrogallol, phloroglucinol,di-, triand tetra-phenylol compounds such asbis(p-hydroxyphenyl)-methane and 2,2-bis(p-hydroxyphenyl)propane; and(6) alkylene oxide adducts of the aforesaid initiators such as propyleneor ethylene oxide adducts of glycerol having a relatively low averagemolecular weight up to about 600. Particularly useful in the preparationof flexible foams generally are polyether polyols having an averagehydroxyl functionality of from about 2.1 to about 4. Such polyols areprovided by the employment of either trihydric or tetrahydric starters,mixtures thereof, or appropriate mixtures containing diol starters. Themore highly functional polyether polyols are usually employed inproviding the semi flexible and rigid foams. The above-describedpolyether polyols are normally liquid materials and, in general, areprepared in accordance with well known techniques comprising thereaction of the polyhydric starter and an alkylene oxide in the presenceof an oxyalkylation catalyst. Usually, the catalyst is an alkali metalhydroxide such as, in particular, potassium hydroxide. The oxyalkylationof the polyhydric initiator is carried out at temperatures ranging fromabout 90C. to about 150C. and usually at an elevated pressure up toabout 200 p.s.i.g., employing a sufficient amount of alkylene oxide andadequate reaction time to obtain a polyol of desired molecular weightwhich is conveniently followed during the course of the reaction bystandard hydroxyl number determinations, as defined above. The alkyleneoxides most commonly employed in providing the reactants encompassed byPolyol I, are the lower alkylene oxides, that is, compounds having fromtwo to four carbon atoms including ethylene oxide, propylene oxide,butylene oxides (1,2- or 2,3-) and combinations thereof. When more thanone type of oxyalkylene unit is desired in the polyol product, thealkylene oxide reactants may be fed to the reaction system sequentiallyto provide polyoxyalkylene chains containing respective blocks ofdifferent oxyalkylene units or they may be fed simultaneously to providesubstantially random distribution of units. A1-

ternatively, the polyoxyalkylene chains may consist essentially of onetype of oxyalkylene unit such as oxypropylene capped with oxyethyleneunits.

A second class ofpolyols that are suitable foruse in preparingpolyurethane foams in accordance with the present invention arepolymer/polyols which, for convenience, are referred to herein as Polyol11. Such reactants are produced by polymerizing one or moreethylenically unsaturated monomers dissolved or dispersed in any of theother types of organic polyol reactants described herein, in thepresence of a free radical catalyst. Especially suitable as thesubstrate polyols for producing such compositions are any of theabovedescribed polyether polyols encompassed by the definition ofPolyol 1. Illustrative of suitable ethylenically unsaturated monomersare vinyl compounds having the en for u a where: R is hydrogen, methylor any of the halogens (i.e., fluorine, chlorine, bromine or iodine);and R is R", cyano, phenyl, methyl-substituted phenyl, carboalkoxy, oralkenyl radicals having from two to six carbon atoms such as vinyl,allyl and isopropenyl groups. Typical examples of such polymerizablemonomers are the following which may be employed individually or incombination: ethylene, propylene, acryloni: trile, methacrylonitrile,vinyl chloride, vinylidene chloride, styrene, alpha-methylstyrene,methyl methacrylate, and butadiene. These and other polymer/- polyolcompositions which are suitably employed either individually or incombination wityh Polyol I are those described in British Pat. No.1,063,222 and U.S. Pat. Nos. 3,304,273, 3,523,093 and 3,383,351, thedisclosures of which are incorporated herein by reference. Suchcompositions are prepared by polymerizing the monomers in the polyol ata temperature between about 40C. and about 150C. employing any freeradical-generating: initiator including peroxides, persulfates,percarbonates, perborates and azo compounds. Illustrative of suitableinitiators are: hydrogen peroxide, dibenzoyl peroxide, benzoylhydroperoxide, lauroyl peroxide and azobis(isobutyronitrile).

The polymer/polyol compositions usually contain from about 5 to about50, and more usually from about 10 to about 40, weight per cent of thevinyl monomer or monomers polymerized in the polyol. Especiallyeffective polymer/polyols are those having the following composition:

A. from about 10 to about 30 weight per cent of a copolymer of (1)acrylonitrile'or methacrylonitrile, and (2) styrene oralpha-methylstyrene, the said copolymer containing from about 50 to andfrom about 50 to 25 weight per cent of monomeric units of 1) and (2),respectively; and

B. fromabout to about 70 weight per cent of one or more of the polyolsencompassed by Polyol I as i the medium in which saidcomponent (A) ispoly merized, the trifunctional polyols such as alkylene oxide adductsof glycerol being especially suitable. These polymer/polyol compositionscontaining components (A) and (B) are the subject of copending U.S.application Ser. No. 176,317, filed Aug. 30, 1971, in the name of David'C. Priest.

Other types of suitable polyol reactants for use in producingcellularpolyurethanes as described herein are polyester polyols providedas the reaction products of: (1) a polyfunctional organic carboxylicacid, and (2) one or more of the aforesaid polyether polyols or one ormoreof the aforesaid polyhydric organic compounds which are reacted withalkylene oxide to produce such polyether polyols. Among the suitablepolycarboxylic acids that can be employed in producing such polyesterpolyols arezthe aliphatic acids which are usually free of reactiveunsaturation such as ethylenic and acetylenic groups, such as, forexample, succinic acid, adipic acid, sebacic acid, azelaic acid,glutaric acid, pimelic, malonic, and suberic acids; cycloaliphatic acidssuch as chlorendic acid; and aromatic poly-basic acids such as phthalic,terephthalic, isophthalic acids and the like.

Also contemplated for use as a polyol reactant of the foam formulationsemployed in the practice of this invention are nitrogen-containingpolyols. Such polyols include lower alkylene oxide adducts of thefollowing amines which may be employed individually or in combination:primary and secondary polyamines such as ethylene-diamine,diethylenetriamine and toluenediamine; and aminoalkanols such asethanolamine, diethanolamine, triethanolamine and triisopropanolamine.Also suitable are mixed starters containing one or more of the aforesaidpolyfunctional amines, aniline, and/or one or more of the polyhydricinitiators employed to produce Polyoll such as dipropylene glycol,glycerol and sucrose. Also illustrative of suitable nitrogencontainingpolyols are aniline/formaldehyde and aniline/phenol/formaldehydecondenstation products. Such amine-based polyols are usually employed inrigid foam formulations.

Other suitable polyols for use in producing polyurethane foams asdescribed herein are: lactone-based polyols prepared by reacting alactone such as epsiloncaprolactone, or a mixture ofepsilon-caprolactone and an alkylene oxide, with a polyfunctionalinitiator such as a polyhydric alcohol, an amine, or an aminoalcohol;phosphorus-containing polyols such as the alkylene oxide adducts ofphosphoric acid, polyphosphoric acids such as triand tetra-phosphoricacids, organosubstituted phosphoric acids such as benzenephosphoricacid; and other polyol reactants known to the polyurethane art.

The beta-amino carbonyl compounds described herein are used withparticular advantage as catalysts in the manufacture of high-resilienceflexible foam. Such foams usually have a resiliency of from about 55 toabout 70 per cent, as measured by standard test procedure ASTM D- 156469. In accordance with a preferred embodiment of this aspect of thepresent invention, the beta-amino carbonyl compounds are employed ascatalytic components of high-resilience foam formulations wherein atleast 40 weight per cent of the total polyol content is constituted of apolyether triol having the following additional characteristics: (a) anaverage primary hydroxyl content of at least 40 mole per cent (for nomore than 60 mole per cent of the less reactive secondary hydroxylgroups); and (b) an average molecular weight of from about 2,000 toabout 8,000. For convenience, this particular class of polyols arereferred to herein as Polyol I-A. Preferably, such polyether triols foruse as components of highresilience formulations contain from about 60to about 90 mole per cent of primary hydroxyl groups and have an averagemolecular weight of from about 4,000 to about 7,000. Consistent withtheir trifunctionality and the aforesaid respective ranges of molecularweight, such polyether triols have hydroxyl numbers from 84 to 21,preferably from 42 to 24. These highly reactive polyether triols areprovided by oxyalkylation of one of the aforesaid trihydric starterssuch as glycerol, with propylene oxide and ethylene oxide. Usually, thetotal ethylene oxide content of the polyether triols encom- 5 passed bythe definition of Polyol l-A is between about 7 and about 20 weight percent, expressed on the basis of total alkylene oxide fed during theoxyalkylation reaction. The high primary hydroxyl content is introducedby capping of the polyoxyalkylene chains with at least a portion of thetotal ethylene oxide feed.

In providing high-resilience foams, the polyether triols included withinthe definition of Polyol l-A may be used as essentially the sole type ofpolyol in the formulation or they may be employed in combination withother polyols to control the degree of softness or firmness of the foamand to vary the load-bearing properties. For example, when softer gradehigh-resilience foams are desired, Polyol l-A may be used in combinationwith polyether diols such as the above-described lower alkylene oxideadducts of a dihydric initiator such as dipropylene glycol. When firmgrades of highresilience foams having enhanced load-bearing proper- 1.from about 40 to about 80 p.p.h.p. of the polyether triols, designatedhereinabove as Polyol l-A; and

2. from about 60 to about 20 p.p.h.p. of polymer/- polyols, designatedherein as Polyol Il-A, prepared by the in situ polymerization of amonomer mixture containing from about 50 to about 75 weight per cent ofacrylonitrile and from about 50 to about 25 weight per cent of styrene,in Polyol LA, the said monomer mixture constituting from about 10 toabout 30 weight per cent of the combined weight of the monomers andPolyol I-A.

The polyisocyanates used in the manufacture of polyurethanes are knownto the art and any such reactants are suitably employed in producingpolyurethane foams in the presence of the beta-amino carbonyl catalystsdescribed herein. Among such suitable polyisocyanates are thoserepresented by the general formula:

' Q )t wherein: i has an average value of at least two and is usually nomore than six, and Q represents an aliphatic, cycloaliphatic or aromaticradical .which can be an unsubstituted hydrocarbyl group or ahydrocarbyl I group substituted, for example, with halogen or alkoxy.For example, Qcan be an alkylene, cycloalkylene, arylene,alkyl-substituted cycloalkylene, alkarylene or aralkylene radicalincluding corresponding halogenand alkoxy-substituted radicals. Typicalexamples of polyisocyanates for use in preparing the polyurethanes ofthis invention are any of the following including mix-' anate,triphenylmethane-4,4',4-triisocyanate, and other organic polyisocyanateknown to the polyurethane art. Other suitable polyisocyanate reactantsare ethylphosphonic diisocyanate and phenylphosphonic diisocyanate. Ofthe aforesaid types of polyisocyanates, those containing aromatic nucleiare generally preferred.

Also useful as the polyisocyanate reactant are polymeric isocyanateshaving units of the formula:

wherein R' is hydrogen and/or lower alkyl and j has an average value ofat least 2.1. Usually, the lower alkyl radical is methyl and j has anaverage value no higher than about 4. Particularly usefulpolyisocyanates of this type are the polyphenylmethylene polyisocyanatesproduced by phosgenation of the polyamine obtained by (50-500centipoises at 25C) liquids having average isocyanato functionalities inthe range of about 2.25 to about 3.2 or higher, and free -NCO contentsof from about 25 to about 35 weight per cent, depending upon thespecific aniline-to-fo'rmaldehyde molar ratio used in the polyaminepreparation.

Also useful as polyisocyanate reactants are polymeric tolylenediisocyanates obtained as residues from the manufacture of thediisocyanates and having a free -NCO content of from about 30 to about50 weight per cent. Other useful polyisocyanate reactants arecombinations of diisocyanates with polymeric isocyanates containing morethan two isocyanate groups per molecule. Illustrative of suchcombinations are: a mixture of 2,4'-tolylene diisocyanate, 2,6-tolylenediisocyanate. and the aforesaid polyphenylmethylene polyisocyanatesand/or the aforementioned residue products.

Of the aforesaid polyisocyanates, those employed with particularadvantage in providing highresilience foams are mixtures containing fromabout 60 to about 90 weight per cent of the isomeric tolylenediisocyanates and from about 40 to about weight per cent of thepolyphenylmethylene polyisocyanates, in order to enhance the average-NCO functionality and thus the reactivity of the reaction mixture. Whenthe highresilience formulations contain diisocyanates as essentially thesole source of reactive -NCO, it is often desirable to include minoramounts, such as up to about l.5

p.p.h.p., of cross-linking agents. Suitable additives for" this purposearediethanolamine, anolamine and triethanolamine.

On a combined basis, the polyol reactant and organic polyisocyanateusually constitute the major proportion by weight of thepolyurethane-forming reaction mixture. In general, the polyisocyanateand polyol reactants are employed in relative amounts such that theratio of total -NCO equivalents tototal active hydrogen equivalent (ofthe polyol and any water, when used) is from 0.8 to 1.5, usually from0.9 to 1.20, equivalents methyldiethof -NCO per equivalent of activehydrogen. This ratio is known as the Isocyanate Index and is often alsoexpressed as a per cent of the stoichiometric amount of polyisocyanaterequired to react with total active hydrogen. When expressed as a percent, the isocyanate Index may be from to l50, and is usually within therange from about to about l20. More usually, the isocyanate Index is nomore than about 1 l5.

The beta-amino carbonyl catalysts may be employed individually or incombination with one another and are present in the foam formulation incatalytically effective amounts. Thus, the total concentration thereofmay vary over a relatively wide range such as from about 0.01 to about 5or more parts by weight (exclusive of any carrier solvents or otheradditives) per parts by weight of the total polyol reactant contained inthe reaction mixture. Usually, this catalytic-component is present in anamount from about 0.05 to about 3.0 p.p.h.p. ln flexible foamformulations, it is usually adequate to employ the betaamino carbonylcatalysts in an amount up to about one p.p.h.p., whereas in rigidformulations, higher concentrations are usually used.

The beta-amino carbonyl catalysts may be employed as the sole type ofamine catalyst of the foam formulations described herein or they may beemployed in combination with one or more tertiary'amines conventionallyemployed as catalysts in producing polyurethanes. Such additionalcatalysts include amines consisting of carbon, hydrogen and nitrogen, aswell as amines consisting of these three elements and oxygen whereinoxygen is present solely as ether or hydroxyl groups. Although theseauxiliary amine catalysts can contain up to 24 carbon atoms, the morecommonly employed compounds contain no more than 12 carbons.Illustrative of such tertiary amines for use in combination with thebeta-amino carbonyl catalysts are: trimethylamine; triethylamine;tributylamine; N,N,N,N- tetramethylethylenediamine;N,N,N',N-tetramethyll,3-butanediamine; N,N-dimethylcyclohexylamine;N,N-dimethylbenzylamine; bis[2-(N,N- dimethylamino)alkyl]ethers such asbis{2-(N,N- dimethylamino)ethyl]ether; triethylenediamine; N-methylmorpholine; N-ethylmorpholine; N-(2- hydroxyethyl)-piperazine;N-methyldiethanolamine; N,N-dimethylethanolamine; and other such conven-,tional tertiary amine polyurethane catalysts. Of the aforesaid tertiaryamines, those containing reactive hydroxyl are often used to serve theadditional function of cross-linking agents. Such alkanolamines areoften used in the manufacture of rigid foams, or to enhancecross-linking density of high-resilience foams based on diisocyanates.

When used, the supplementary tertiary amine catalysts may be present inthe foam formulation in an amount within the aforesaid ranges definedwith respect to the beta-amino carbonyl catalysts, although usually thetotal amount of supplementary amine is no more than about 1 p.p.h.p. itis to be understood that the betaamino carbonyl catalyst and thesupplementary tertiary amine, when used, may be added to the formulationas separate streams or in preblended form.

Illustrative of suitable blended catalysts provided by the presentinvention and which are especially useful as components of water-blown,flexible foam formulations including high-resilience systems, are thosecontaining from about 10 to about 90 weight per cent-0f the beta-aminocarbonyl compounds and correspond ingly from about 90 to about weightper cent of either bis[2-(N,N-dimethylamino)ethyl]ether,triethylenediamine, or the bis-amino ether plus triethylenediamine. Itis to be understood that the said weight percentages are based on thetotal weight of the blended catalysts, exclusive of carrier solvents orother additives. These blends are added to the foam formulations in anamount sufficient to provide the beta-amino carbonyl catalyst andauxiliary amine within the aforesaid respective ranges of concentration,that is, between about 0.01 and about 5 p.p.h.p.

From the standpoint of providing an effective catai lyst system, thebeta-amino carbonyl catalyst may be used, as included in the foregoingdescription, in combination with N-alkylmorpholines such as N-ethylmorpholine. The latter compound is presently used in commercialpractice in relative high concentrations (up to about 2.0 p.p.h.p.) as acatalytic component of molded high-resilience formulations in order toprovide foams having good mold-release characteristics. In view of thepresent discovery that such foams can be produced by employing thebeta-amino carbonyl catalysts described hereinwithout the necessity ofusing N-ethylmorpholine, the latter catalyst may be completelyeliminated, thereby avoiding the obnoxious residual foam odor associatedtherewith. It is to be understood, however, that N-ethylmorpholine maybe used as a component of the foam formulations described herein withoutdeparting from the scope of this invention. When used, the level of suchN- alkylmorpholine catalysts is desirably kept to a minimum such as nomore than about 0.30 p.p.h.p.

It is to be understood that the beta-amino carbonyl catalysts employedin accordance with the present invention, as well as blends basedthereon, may beintroduced to the foam formulations in undiluted form oras solutions in suitable carrier solvents such as diethylene glycol,dipropylene glycol and hexylene glycol. The

supplementary amine catalysts are also often employed in such carriersolvents.

Other useful carrier solvents for the catalysts described herein arelower alkylene oxide adducts of monohydric or polyhydric starters suchas butanol, dipropylene glycol and glycerol. Such solvents (or diluents)generally include adducts containing from about 3 to about 30oxyethylene or oxypropylene units, mixtures of such adducts, as well asadducts provided by reaction of the starter with ethylene oxide andpropylene oxide, fed either as a mixed feed or sequentially. Among thesuitable organic carrier solvents of this type are the ethyleneoxide-propylene oxide adducts of butanol having the average formula, C H(OC l-l- ,),,(OC l-l ,),,Ol-l, wherein s and u may each have an averagevalue from about 3 to about 30. Preferably, the values of and u are suchthat the average molecular weight of these fluids is not substantiallygreater than about 2,000 and the oxyethylene content is from about 20 toabout 80 weight per cent, based on total polyoxyalkylene content.Usually, the weight per cent of oxyethylene is about the same as theweight per cent of oxypropylene.

Also included within the scope of the present invention is the use'ofthe beta-amino carbonyl catalysts in combination with organicsurfactants. When used, the organic surfactant is usually a non ionicsurfactant such as: the polyoxyalkylene ethers of higher alcohols havingfrom 10 to 18 carbon atoms including mixtures thereof; andpolyoxyalkylene ethers of alkylsubstituted phenols in which the alkylgroup can have from six to 15 carbon atoms. The length of the etherchain is such that appropriate hydrophilic character is provided tobalance the hydrophobic portion derived from the alcohol or phenol andrender the compound miscible with water. The chain may containoxyethylene. units either as essentially the sole type of unit oroxyethylene in combination with a minor amount of oxypropylene. It ispreferred that the hydrophilic portion of the non ionic surfactants becomposed essentially of oxyethylene monomeric units. Usually the averagenumber of such -OC H.,- units ranges from about 4 to about 20, althoughupwards of 30 such unitscan also be present.

' Typical examples of non ionic surfactants which can be used incombination with the beta-amino carbonyl catalysts employed in thepractice of this invention are the adducts produced by reaction of fromabout 4 to about 30 moles of ethylene oxide per mole of any of thefollowing hydrophobes including mixtures thereof: n-

undecyl alcohol, myristyl alcohol, lauryl alcohol, trimethyl nonanol,tridecyl alcohol, pentadecyl alcohol, cetyl alcohol, oleyl alcohol,stearyl alcohol, nonylphenol, dodecylphenol, tetradecylphenol, and thelike. Es-

pecially suitable for use as the carrier medium'for the beta-aminocarbonyl catalysts described herein are the ethylene oxide adducts ofnonylphenol having the average composition, C H, -C H -(OC H ),,-OH,wherein h has an average value from about 4 to about 20, inclusive ofwhole and fractional numbers, such as 6, 9, 10.5 and 15.

The above-described solution compositions may contain from about 10 toabout weight per cent of total beta-amino carbonyl catalyst (inclusiveof supplementary tertiary amine catalyst, when used), based on thecombined weight of catalyst, solvent and/or organic surfactant,depending upon whether the catalyst is employed in combination witheither one or both of the solvent and organic surfactant.

It is often desirable to include as a further component I of the foamformulation a minor amount of certain metal catalysts, particularlyorganic derivatives of tin including stannous and stannic compounds.Such metal co-catalysts-are well known to the art and are usuallyemployed in producing polyether polyol-based polyurethanes. Illustrativeof suitable organic tin compounds are the following which may beemployed individually or in combination: stannous salts of carboxylicacids such as stannous octoate, stannous oleate, stannous acetate andstannous laurate; dialkyltin dicarboxylates such as-dibutyltindilaurate, dibutyltin diacetate, dilauryltin diacetate, dibutyltin di(2-ethylhexanoate) and other such tin salts as well as dialkyltin oxides,trialkyltin oxides, tin mercaptides such as, for example, di-n-octyl tinmercaptide, and the like. When used, the amount of such metalco-catalysts ranges from about 0.001 to about 2 parts by weight perparts by weight of total polyol reactant. In flexible foam formulations,the metal co-catalyst is preferably used in an amount from about 0.01 toabout 0.6 p.p.h.p., and most preferably in an amount no more than about0.5 p.p.h.p.

Foaming is accomplished by the presence in the reaction mixture ofvarying amounts of a polyurethane blowing agent such as water which,upon reaction with isocyanate, generates carbon dioxide, in situ, or

through the use of blowing agents which are vaporized by the exotherm ofthe reaction, or by a combination of the two methods. These variousmethods are known in the art. Thus, in addition to or in place of water,other blowing agents which can be employed in the process of thisinvention include methylene chloride, liquefied gases which have boilingpoints below 80F. and above 60F., or other inert gases such as nitrogen,carbon dioxide added as such, methane, helium and argon. Suitableliquefied gases include aliphatic and cycloaliphatic fluorocarbons whichvaporize at orbelow the temperature of the foaming mass. Such gases areat least partially fluorinated and may also be otherwise halogenated.Fluorocarbon agents suitable for use in foaming formulation of thisinvention include: trichloromonofluoromethane; dichlorodifluoromethane;l,1 dichlorol -fluoroethane; 1,2,2-trifluoro-l ,1 ,2- trichloroethane;1,1 l trifluoro-2-fluoro-3,3-difluoro- 4,4,4-trifl-uorobutane;hexafluorocyclobutene; and. octafluorocyclobutane. Another useful classof blowing agents include thermally-unstable compounds which liberategases upon heating, such as N,N'-dimethyl- N,N-dinitrosoterephthalamide,and the like.

Generally, the blowing agent is employed in an amount from about 1 toabout 45 parts by weight per 100 parts by weight of total polyolreactant, the particular blowing agent and amount thereof depending uponthe type of foam product desired. Flexible foam formulations includingthose which favor formation of highresilience foam, are most usuallywater blown, although a minor proportion such as up to about weight percent of total blowing agent may be constituted of a fluorocarbon such astrichlorofluoromethane. Flexible foam formulations usually contain nomorethan about 10 p.p.h.p. of water. For rigid formulations, blowingaction is usually supplied employing a fluorocarbon in a relatively highproportion such as from about 10 to about 45 p.p.h.p., either as thesole type of agent or in combination with a minor amount of water suchas up to about 10 weight per cent of total blowing agent. The

selection and amount of blowing agent in any particular foam formulationis well within the skill of the cellular polyurethane art. I

In producing cellular polyurethanes in accordance with the method ofthis invention, a minor amount of an organosilicone surfactant may alsobe present as an additional component of the polyurethane-formingreaction mixture. When used, such surfactants are usually present inamounts up to about 5 parts by weight per 100 parts by weight of totalpolyol reactant.

Among the suitable classes of surfactant are thepolysiloxane-polyoxyalkylene block copolymers wherein the respectiveblocks are joined through silicon-to-carbon orsilicon-to-oxygen-to-carbon bonds and the respective polyoxyalkyleneblocks are bonded to different silicon atoms of the polysiloxanebackbone to form a comb-like structure. Usually, the polysiloxane blocksare trialkysiloxy-endblocked. In addition to siloxy units to which thependant polyoxyalkylene chains are bonded, the polysiloxane backbone isformed of difunctional siloxy units wherein the respective two remainingvalences of silicon are satisfied by.

bonds to organic radicals. Illustrative of such organic radicals are thehydrocarbyl groups having from one to 12 carbon atoms including alkyl,aryl, aralkyl, bicycloheptyl and halogensubstituted derivatives of suchgroups. The polyoxyalkylene blocks are usually constituted ofoxyethylene units, oxypropylene units or a combination of such units,and the polyoxyalkylene chains are hydroxyl-terminatedor capped with amonovalent organic group such as alkyl, aryl, aralkyl, acyl, carbamyland the like. Especially useful as stabilizers of flexiblepolyether-based polyurethane foams are the block copolymers described inU.S. Pat. No. 3,505,377, an application for reissue of which was filedon Nov. 18, 1971 as Ser. No. 200,242 of Edward I... Morehouse, now U.S.reissue Pat. No. 27,541. The copolymers of the latter patent containfrom 40 to 200 dimethylsiloxy units as essentially the sole type ofdifunctional unit, and from 15 to 60 weight per cent of the oxyalkylenecontent of the polyoxyalkylene blocks is constituted of oxyethylene.Also useful as stabilizers of flexible, polyether-based polyurethanefoam including flame-retarded foam, are the block copolymers describedin U.S. Pat. No. 3,657,305. The polysiloxane backbone of theorganosilicones of the latter patent, contains an average of from 10 to'200 dimethylsiloxy units in combination with from 1 to 50methylaralkylsiloxy units such as, in particular,methylphenylethylsiloxy units [(CH )(C I-I CI-I CH )SiO]. Other useful.foam stabilizers for flexible polyether based foam are the blockcopolymers described in U.S. Pat. No. 3,686,254. Particularly usefulstabilizers of flexible polyester-based polyurethane foam are thesurfactants described in' U.S, Pat. No. 3,594, 334. a

Asecond type of foam-stabilizing component which can be present in theformulations described herein are the branched block copolymersdescribed in U.S. Pat. No. 2,834,748. Organosilicone foam stabilizersdescribed in the latter patent include those containing a trifunctionalsiloxy unit to which three polyoxyalkylene blocks are bonded throughdialkyl-substituted siloxy units. A preferred group are those having theformula, MeSi[OSiMe -),(OC,,I-l OX] wherein Me is methyl, x has a valueof at least one, a is from 2 to 3, v has a value of at least 5, and X ishydrogen or a monovalent hydrocarbyl group such as lower alkyl, butylbeing especially suitable.

Particularly useful as foam-stabilizing components of flame-retardedflexible polyurethane formulations are the block copolymers wherein thepolysiloxane blocks are trialkylsiloxy-endblocked and containreoccurring difunctional dialkylsiloxy monomeric units in combinationwith reoccurring difunctional cyanoalkylalkylsiloxy orcyanoalkoxy-alkylsiloxy monomeric units, the mole ratio of thedialkylsiloxy units to the cyano-substituted siloxy units being about10-200- :3-100, and wherein the polysiloxane and polyoxyalkylene blocksare joined through an Si-C or an Si-O-C linkage, and from about 20 toabout 65 weight per cent of the oxyalkylene content of thepolyoxyalkylene blocks is constituted of oxyethylene units. These blockcopolymers are described and claimed in copending application Ser. No.279,883, filed Aug. 11, 1972, in the names of Bela Prokai and BernardKanner. A preferred class of such surfactants are thecyanopropylsubstituted block copolymers having the average formula, I

Me Si o (M61810) MeSi 0 L M a Si 0 SlMe3 L ((lHm-l LW0(C.H1- )b a o...l| wherein: Me represents methyl; W represents a monovalenthydrocarbyl group (R'-), an acyl group [R'C(O)-] or a carbamyl group[R'N H C (O)-] wherein R has from one to 12 carbon atoms; x has anaverage value of from about 20 to about 100; y has an average value offrom about 4 to about 30; z has an average value of from about 2 toabout a has a value of from 2 to 4, provided from about to about 65weight per cent of the oxyalkylene units of the polyoxyalkylene chain,-(C,,H ,,O),,-, are constituted of oxyethylene; and b has an averagevalue such that the average molecular weight of the polyoxyalkylenechain is from about 1,000 to about 6,000.

Because of the high reactivity of high-resilience foam formulations, thefoams are generally self-stabilizing and can be obtained without the useof stabilizing agents. However, it is usually desirable to include asilicone surfactant as an additional component of such formulations inorder to minimize the tendency of the foam to settle and to control celluniformity. Particularly effective for this purpose are the relativelylow molecular weight polyoxyalkylene-polysiloxane block copolymersdescribed and claimed in copending application Ser. No. 84,181, filedOct. 26, 1970, of Edward L. Morehouse now U.S. Pat. No. 3,741,9 l 7.Especially suitable as components of high-resilience formulations arethe block copolymers described therein having the rmu a.

wherein: x has an average value of from 2 'to 7; y has a value from 3 to10; z has an average value from 2 to 6; a and d each has a value from 2to 4; and R is a monovalent hydrocarbon radical such as alkyl, aralkyland aryl radicals, or an acyl group.

Also suitable as organosilicone components of highresilience foamformulations are the relatively low molecular weight aralkyl-modifiedpolymethylsiloxane oils described and claimed in copending applicationSer.

No. 305,713, filed Nov. 13, 1972, in the name of Ed- I ward L.Morehouse, and entitled, Polyether Urethane Foam.

When used, the organosilicone component is usually present inhigh-resilience formulations in an amount between about 0.025 and about2 parts by weight per 100 parts by weight of total polyol reactant.

Illustrative of suitable surfactant components of rigid foamformulations are copolymers wherein the polyoxyalkylene blocksarehydroxyl-terminated such as those described in U.S. Pat. No. 3,600,418.

The beta-amino carbonyl catalysts described herein are also effectivecatalytic components of flameretarded foam formulations. Theflame-retardants can be chemically combined in one or more of the othermaterials used (e.g., in the polyol or polyisocyanate), or they can beused as discrete chemical compounds added as such to the foamformulation. The organic flame-retardants preferably contain phosphorusor halogen, or both phosphorus and halogen. Usually, the halogen, whenpresent, is chlorine and/or bromine. Flame-retardants of the discretechemical variety include: 2,2-bis(bromomethyl)-1,3-propanediol (alsoknown as dibromoneopentyl glycol); 2,3- dibromopropanol;tetrabromophthalic anhydride; brominated phthalate ester diols such asthose produced from tetrabromophthalic anhydride, propylene oxide andpropylene glycol; tetrabromobisphenol-A; 2,4,6- tribromophenol;pentabromophenol; brominated anilines and dianilines;bis(2,3-dibromopropyl)ether -dibromopropyl)ether of sorbitol;tetrachlorophthalic anhydride, chlorendic acid; chlorendic anhydride;diallyl chlorcndate; chlorinated maleic anhydride; 5tris(2-chloroethyl)phosphate [CICH CH O) P(O)];

tris(2,3-dibromopropyl)phosphate; tris( l ,3- dichloropropyl)phosphate;I tris( l-bromo-3- chloroisopropyl)phosphate; tris(1,3-

dichloroisopropyl)phosphate; bis(2,3-dibromopropyl) phosphoric acid orsalts thereof; oxypropylated phosphoric and polyphosphoric acids; polyolphosphites such as tris(dipropylene glycol)phosphite; polyolphosphonates such as bis(diprop'ylene glycol)hydroxymethyl phosphonate;di-poly(oxyethylene)hydrox- 20 pounds having the formulas:

and

Other suitable flame-retardants comprise halogencontaining. polymericresins such as polyvinylchloride resins in combination with antimonytrioxide and/or other inorganic metal oxides such as zinc oxide, asdescribed in U.S. Pats. No. 3,075,927; 3,075,928; 3,222,305; and3,574,194. It is to be understood that other flame-retardants known tothe art may be used and that the aforesaid compounds may be employedindividually or in combination with one another.

When used, the flame-retarding agent can be present in the foamformulations described herein in an amount from about 1 to about 30parts by weight per 100 parts by weight of the polyol reactant, theparticular amount employed depending largely on the efficiency of anygiven agent in reducing flammability.

If desired, other additional ingredients can be employed in minoramounts in producing the polyurethane foams in accordance with theprocess of this invention. illustrative of such additives that can beemployed are: the aforementioned cross-linking agents such as glycerol,diethanolamine, triethanolamine and their oxyalkylene adducts; additivesto enhance loadbearing properties such asmethylene-di-orthochloroaniline (MOCA); as well as fillers, dyes,pigments, anti-yellowing agents and the like.

The cellular urethane polymers of the invention may be formed inaccordance with any of the processing techniques known to thepolyurethane art such as the one-shot, quasi-prepolymer and prepolymertechniques. For example, in accordance with the oneshot process, foamedproducts are produced by carrying out the reaction of the polyisocyanateand the polyol reactants in the presence of the beta-aminocarbonyl-containing catalyst systems described herein, simultaneouslywith the foaming operation. This onestep process is usually employed inproducing flexible foam including high-resilience foam, although it isalso applicable to rigids. In preparing foamed products in ymethylphosphonate; di-poly(oxypropylene)phenyl.

accordance with the quasi-prepolymer technique, the polyisocyanate isfirst reacted with a portion of the polyol reactant to give a producthaving a high percentage of free NCO groups (e.g., from 20 to 50 percent), and the product is subsequently foamed by reaction duced inaccordance with the present invention are useful as textile interliners,cushioning material, mattresses, paddings, carpet underlay, packaging,gaskets, sealers, thermal insulators and the like.

The following examples are offered as further illuswith additionalpolyol and foaming agent in the prestrative of the present invention andare not to be conence of the beta-amino carbonyl catalysts. In the pretd as d l li iti P y technique, the polyisoeyahate is reacted withExamples l-l0 describe the preparation of illustraa Slightly l thahStetehtometrte q y of the p y tive beta-amino carbonyl catalysts,designated herein reactant to form a P p y having 310w Percentage, asAmine Catalysts I-X, respectively, which were em- -g from 1 to 10 Pcent) of free g P ployed as catalyst components in the polyurethanelowed y reaction of the Prepolymet with a blowing foam preparations ofthe remaining examples. Of these, agent such as water in the presence ofthe catalyst sys- Amine Catalysts 1v v VI and v1] arc ncvc] mtemsdescribed herein to form the cellular material. pounds In Examples 1 1 namine reactant was b- These Var 10115 mum-Stage methods are more usuallyP stantially anhydrous and the reaction media contained plied to rigidformulatiohsless than about 5 weight per cent water,'expressed on In gfinal p g 0f the foam Products the basis of amine reactant. The yieldsof product are iS achieved y a o g the fOam to Stand at ambient based onthe number of moles of reactant present in the temperatures until atack-free product is obtained, or li i i amount by subjecting the foamto elevated temperatures up to about 500F. in order to achieve morerapid curing. In EXAMPLES view of the higher reactivity of thecombination of re- I accordance i h these examples b actams mp inProducing high-resilience foams, dialkylamino-N,N-dialkylamides,designated herein as however? a sufficiently high degree of curing AmineCatalysts LIV, respectively, were preparedby achieved during foamformation without the necessity the reaction f Secondary amines (R' A) d0f subjecting the foam to eohvehtiohal high p alkyl esters of alpha,beta-unsaturated carboxylic acids ture -g- 3000-500?) Post-CuringProcedures which (Reactant B) in the presence of phenothiazine (0.7 areotherwise applied in the commercial manufacture gram) andp-methoxyphenol (0.7 gram) as inhibitors, 0f flexible teams from lesshighly reactive flexible foam under elevated temperature and pressureconditions in formulations. a stainless steel rocker bomb. Theparticular reactants,

In the specific application of the betaamino amides relative proportionsthereof and reaction conditions of and beta-amino esters describedherein as catalytic temperature, pressure and time are given in Table 1.components f l d i nili f f r l After the indicated reaction time, thereactors were ticns, n ld i h d i h h f bl ti n cooled and therespective reaction mixtures were transmixture either at ambienttemperature or pre-heated to ferred to a Still except that, Example thereaction a temperature f f m about 70} to about 200F,, i mixture waspartially stripped of volatiles after disan amount sufficient to atleast completely fill the charge from the pressure reactor and a port omold. The mold is then closed and the reaction mixture grams) of thepartially stripped material was combined is allowed to foam and cureitself. In view of the excelith phcn hi zi g pyp lent moldreleasecharacteristics of the high-resilience gram) and Humble 1243 oil asapot-boiler (20 grams). foams produced in accordance with the presentinven- In each example, the respective products were recovtion, thefoamed product is readily removed from the ered by distillation underthe temperature and reduced mold without substantial damage to the foamsurface. pressure conditions specified in Table 1. Of these prod- Thedemolded foam is suitable for end-use application ucts, Amine CatalystsI, II and III are known comwithout further curing. It is to beunderstood, however, o ds and w re prod ced in a purity of about -98 h tsuch foam y be Subjected to further ehthlg, as per cent, as indicated bygas chromatographic analysis. desll'ed- Amine Catalyst 1V is a novelcompound and its struc- The end-use applications of cellularpolyurethanes ture was verified by infrared and nuclear magnetic resarewell known. Thus, the polyurethane foams ,proonance spectroscopy.

TABLE] I Example Beta-Amino Amide Catalyst Reactant A Reactant B Temper-Pressure Time Product Recovery No. (grams) (grams) alure (p.s.i.g-)(hours) No. (CJ C. mm.Hg Yield% I l J-dimcthyluminu-N, -dimcthylpru-Dimcthyluminc Elhylncrylme ltitl-ltlll ltlg itlll 20 103-105 H)pionuinitle (4W) (300) tcnnun-cmcnrctomtcunz 2 II 3-dimethylaminol-methyl-N, Dimethylamine Methyl mega 1 720 40 -500 20 61-62 3 44N-dimethylpropionamide crylate (I00) 525 2 Ee'PhQtQZPlQHsh 3 III3-diethylamino-N, N-diethylpro- Diethylamine Methyl acrylate -200200-320 32 90-91 3 22 Dimethylamine N-dimethylbutyramide (1 l7) Methylcrotonate 34 EXAMPLE Preparation of3-Diethylamino-N,N-Diethylpropionamide In accordance with this example,anhydrous diethylamine (44 grams) and N,N-dimethylacrylamide (60 grams)were heated at reflux temperature (about S6-60C.) for 48 hours. Afterthis period of time, the reaction mixture was subjected to distillationto separate unreacted amine and amide followed by recovery of productin.86 per cent yield at 70C. and 2 mm. mercury pressure. The liquidproduct (purity about 95 per cent)'is designated herein as AmineCatalyst V, and has the formula, (C H N-CH CH C(O)N(CH The structure ofthis novel product was confirmed by infrared functional analysis andpurity by gas-liquid chromatographic analysis.

EXAMPLE 6 Preparation of 3-(N-Morpholino)-N,N-DimethylpropionamideMorpholine (45 grams) was added dropwise to a stirred reaction flaskcontaining N,N- dimethylacrylamide (50 grams). After the addition wascompleted, the reaction mixture was stirred for 24 hours at 30 -70C.After this period of time, the reaction mixture was heated at l 10C. and10 mm. mercury pressure to remove unreacted starting materials. Theremaining material was a viscous liquid and was recovered in a 95 percent yield. This residue product contains about 98 weight per cent ofthe novel compound,

and is designated therein as Amine Catalyst VI. A sample of thismaterial was distilled at 1l4-l C. and 1. mm. mercury pressure withoutappreciable decomposition. The structure was verified by infrared andnuclear magnetic resonance spectroscopy.

EXAMPLE 7 O NHICH:CHzN

as determined by infrared and nuclear magnetic resonance spectroscopyand elemental analysis. Anal. Calcd. for C, H N.,O C, 59.1; H, 9.9; N,19.7. Found: C, .-0 ns! 53-45% 9 n 952; ,a d. -4.- Ihi novel product isdesignated herein as Amine Catalyst VII.

EXAMPLE 8 Preparation of Ethyl 3-( N,N-Dimethylamino)propionate (CH NCHCH C(O)OC H as verified analytically by infrared spectroscopy.

v EXAMPLE 9 Preparation of Ethyl 3-(N,N Diethylamino)propionate Thefollowing materials were charged to the reaction vessel: anhydrousdiethylamine (292 grams); ethyl acrylate (200 grams); phenothiazine (1.0gram); and pmethoxyphenol 1.0 gram). This mixture was heated at reflux(about 56-60C.) for 24 hours. At the end of this period, unreacted aminewas removed by distillation. The product was recovered at -8lC. and 10mm. mercury pressure in a yield of 96 per cent. The product isdesignated herein as Amine Catalyst IX and verified analytically byinfrared spectroscopy.-

EXAMPLE 10 Preparation of 2-(N,N-dimethylamino)ethyl 3-(N',

Nf-dimethylamino)propionate v Anhydrous dimethylamine (19.8 grams) wasadded dropwise to 2-(N,N-dimethylamino)ethyl acrylate (31.5 grams) in amagnetically-stirred, ice-cooled reaction vessel at such a rate that thetemperature did not exceed 40C. The addition of dimethylamine wascomplete in about 10 minutes. After allowing the reaction;

mixture to stir overnight at room temperature, it was subjected toreduced pressure (about 20 mm. Hg) to remove unreacted dimethylamine.Gas-liquid chromatographic analysis indicated that the residue productwas 96.5 per cent pure. The structure of the product,

CH3 /CH3 N--CH:CHzC-O CHaCHr-N was verifiedspectroscopically (nuclearmagnetic resonance and infrared) and by elemental analysis. Anal. Calcdfor C I-I N O C, 57.4; H, 10.6; N, 14.9. Found: C, 57.3; H, 10,5; N,14.8. This product-is designated herein as Amine Catalyst X.

In the examples which follow, molded and freerise cellular polyurethaneswere prepared employing the above-described Amine Catalysts I-X ascatalytic components of a variety of foam formulations. In someexamples, these beta-amino amide and ester catalysts were used as thesole tertiary'aminecatalytic component of the reaction mixtures whereasin other instances they were used as components of mixed cataples 11-16, the procedure employed was that described below as Foam ProcedureI. The manipulative steps involved in the preparation of the free-risefoams of Examp'les 17 46 were'as described under Foam Procedure II. FOAMPROCEDURE I An aluminum mold (4 inches or 2% inches X 15 inches X 15inches) is prepared by first waxing lightly with Brulin PermamoldRelease Agent and then preheating in :1 140C. oven for about 10 minutesto raise the temperature of the mold to l75200F. Excess mold-releaseagent is wiped off and the mold is allowed to cool to 120F. beforefoaming. The initial mixing of the components of the foam, formulationis started when the mold is cooled to about 130F. The purpose 'ofpre-heating the mold to the initial high temperature reactant is thenweighed into the mixture of other components, stainless-steel bafflesdesigned for the )-gallon carton are inserted, and mixing is continuedfor 5 seconds. The carton is then lowered to allow the mixer to drain,and the contents are quickly poured into the mold. The mold lid isclosed and clamps are placed around the mold to permit flashout. Exittime is observed and defined as the time when all four holes of the moldare full, that is, when the foam begins to exude from all four holes ofthe mold. Pop time is observed and defined as the time when extrudedparts stop bubbling. The 4 inch -mold is demolded after standing at roomtemperature for minutes whereas the 2. /2 inch mold is demolded after 8minutes. After trimming around the edges with scissor, the foam'sampleis weighed before running through rollers four times to crush cellsopen, and is then allowed to cure for three days at room temperaturebefore being submitted for physical property measurements. FOAMPROCEDURE II The polyol and polyisocyanate reactants and surfactant(and, when employed, the flame-retradant and cross-linking agents) areweighed into a -gallon, 5 inch diameter, cyclindrical cardboard carton.The water and catalytic amine components are measured and blendedtogether in a small beaker. The tin catalyst is measured into ahypodermic syringe. Eleven stainless-steel baffles'are inserted into thecarton and centered on a drill press equipped with a 1.65-inch, 4-

blade turbine. A timer is pre-set for a total of 90 seconds. The mixeris started at 2,400 revolutions per minute and continued for 60 seconds,except that in those formulations containing polymer/polyols, the mixeris started at 3,000 revolutions per minute. The mixer is stoppedmanually for a IS-second de-gassing period. .At 75 seconds on the timer,mixing is continued for 5 sec onds before adding the aqueousamine'premix. Mixing are recorded which terms denote the interval oftime from the formation of the complete foam formulation to: (l) theappearance of a creamy color' in the formulation, and (2) the attainmentof the maximum height of the foam, respectively. The foamis allowed tostand at room temperature for about one day before being submitted forphysical property measurements. I

The physical properties which were determined for the flexible foamsproduced in the examples and control runs were measured in accordancewith the standardized test procedures given below.

Porosity .(Air), which is a comparative measurement of the degree ofopenness of the cells of flexible foams,

'was determined in accordance with the following test procedure: Thetest specimen of foam (4 inch X 4 inch X k inch) is compressed betweentwo pieces of flanged plastic tubing (2% inch ID.) of an air porosityassembly maintained under an air pressure of 14.7 pounds. Air is drawnthrough the thickness (A inch) of the foam specimen at a velocitycontrolled to maintain a differential pressure of 0.1 inch of wateracross the thickness dimension. The air flow necessary to develop therequisite pressure differential is recorded and the air flow per unitarea of the foam specimen is reported as the porosity of the foam.

Resiliency of both the molded and free-rise foams was determined inaccordance with ASTM D--l5- 64-69.

Density, Tensile Strength, Elongation, Tear Resistance and CompressionSet were measured as described under l) ASTM D-2406-68 for the moldedfoams produced in accordance with Foam Procedure I, and (2) ASTM D-l56469 for the free-rise foams produced in accordance with Foam ProcedureII.

Indentation Load Deflection (lLD Values) to 25 percent and 65 percentdeflections were measured in accordance with (l) ASTM D-2406-68 for themolded foam samples, the thickness of the sample being 2-% inch or 4inch depending'upon whether the 2-% or 4 inch mold was used, and (2)ASTM D'1564-69 for the free-rise foams, the test sample being cut to a 4inch thickness. Return Value is the percentage ratio of the loadrequired to support the return 25 percent indentation after 1 minute ascompared to the load required to support the initial 25 percentindentation after l minute. Load Ratio is the ratio of the 65 percentand 25 percent ILD values,'respectively.

The following Examples 1 l-l6 demonstrate .the efficacy and advantagesof beta-amino amide and ester catalysts described herein when employedas direct replacements for N-ethylmorpholine in high-resilience foamformulations.

EXAMPLES 11 and 12 ployed in Examples 1 1 and 12 and Control Run K-l isgiven in Table II which follows.

TABLE 11 FOAM FORMULATION A Parts By Weight Control Component Examples 11 and I2 Polyol A: An ethylene oxide-capped, glycerolstartedpoly(oxypropylene) triol having a Hydroxyl No. of about 34, a molecularweight of about 5000, and a primary hydroxyl content of 70-75 mole percent.

Poly Q: A polymer/polycthcr polyol having a Hydroxyl No. ol'about 28 andbased on (parts by weight); styrene (l), acrylonitrile (l0) and Polyol A(80). produced by polymerizing said monomers in Polyol A.

Polyisocyanate A: A mixture of: (l) 80 weight per cent of the 2,4- and2,6-isomers of tolylene diisocyanate, the weight ratio of said isomersbeing 80:20, respectively; and (2) weight per cent of apolyphenylemthylene polyisocyanate having an average -NCO functionalityof 2.7 and a free -NCO content of 30.5-32.3 weight per cent.

Water Dibutyltin dilaurate Surfactant A /1/ Surfactnat B /2/ 0.80 NoneNone A phenylethyl-modifed polymethylsiloxane oil having the averagecomposition.

Me SiO(Me,SiO),[(C H,,C l1 )(Me)SiO],,SiMe

wherein Me represents methyl and the average values ofx and y are 3.0and 1.5, respectively.

Same as Surfactant A, except average values of x and y are 3.8 and 1.9,respectively,

The foams of Examples 1 l and 12, designated for convenience as FoamsNos. 1 and 2, respectively, aswell as Control Foam K-l, were preparedfollowing Foam Procedure I, employing the 4 inches X 15 inches X 15 inchaluminum mold heated to 120F. Upon completion of foam formation, ControlFoam K-l was easily removed from the mold after 10 minutes residencetime and foam surface and freedom from tendency to shrink wereexcellent. However, the odor level emanating from the freshly demoldedfoam was very high and, although dimishing in intensity with time, thisodor persisted for several hours. With respect to Foam No. 1,-

demold characteristics were also excellent and the cellular structurewas fine (as opposed to coarse). In the case of Foam No. 2, demoldcharacteristics were good and, although the foam surface structure wasnot as good asv that of Control Foam K-l of Foam No. 1, it wassatisfactory. With respect to both Foam Nos. 1 and 2,

the odor level emanating from the freshly demolded foam was very low andclearly an improvement over the control foam. These and other results aswell as physical property data of the respective foams are given inTable Ill.

TABLE III HIGH-RESILIENCE FOAM (Molded) None None None 0.20

None

Table lll-Continued Exit Time, seconds i I 61 53 59 Pop Time, second 121Hot Foam Odor High Low Low Eoam Properties Basalcell structure Good GoodFair Resilience, ball rebound 63 64 64 Prosotiy. ft."""""-"- 61 53.150.6 Denisty, lbs/ft. 1.96 1.90 1.93 lLD (4f), lbs./50 in,

25% deflection 22.3 20.3 24.2 65% deflection 62.0 56.0 63.0 25% return17.3 16.0 19.0 Return value, 77.6 78.8 78.5

Load Ratio 2.78 2.76 2.62 Compression Sets,

50% After Humid Aging /3/ 26.5 24.9 24.2 Tensile strength, p.s.i. 24.022.6 21.8 Elongation, 199 204 192 Tear Resistance lbs./in. 2.41 2.222.17 Humid Age Load Loss, /3/ 22.4 20.6 20.2

[H 3-dimethyIamino-N,N-dimetliylpropionamidev /2/2-(N,N-Dimcthylamino)ethyl 3-dimethy1aminopropionate. /3/ Five hours atC. in 100% relative humidity.

The results of Table III show that the improvement of low residual foamodor afforded by the catalysts of this invention is achieved withoutsacrifice of the good overall combination of physical propertiespossessed by the control foam. Further. as evinced by the interval oftime required for the foam to exude from the mold. the reactivity of therespective reaction mixtures containing Amine Catalysts l and X wasexcellent even though the concentration of these catalysts was only onefourth the concentration (on a weight basis) of N- ethylmorpholine. Infact, as reflected by comparison of the respective exit times, thereactivity of the formualtion containing3-dimethylamino-N,N-dimethylpropionamide (Example 1 l in an amount of0.20 part per 100 parts of total polyol (p.p.h.p), was 12-14 per centThe foams of Examples 13-16, designated for convenience as Foam Nos.3-6, respectively, as well as Control Foam K-2 were prepared followingFoam Procedure 1, employing the 2- /z inch X 15inch X 15 inch aluminummold heated to 120F. Upon. completion of foaming, it was found that ineach instance demold characteristicswere excellent as reflected by lackof foam tenderness and ease of demolding. The surface structure ofControl Foam K-2 and Foam Nos. 3-6 was also good. However, the odorlevel emanating from the freshly demolded control foam was high. Withrespect to Foam Nos. 3-6, on the other hand, hot foam odor was low andclearly an improvement over that of the control foam. Other results andfoam physical property The results of Table V show that the improvementin hot foam odor realized by use of Amine Catalysts II-V in place ofN-ethylmorpholine was achieved without impairment of the overallcombination of physical properties possessed by the control foam. Thus,the resiliency and porosity of Foam Nos. 3-6, were at least as good asthat of the control foam and their loadbearing, compression set andother properties were also good. In addition to the improvement in hotfoam odor, the humid age load loss of Foam Nos. 3-6 was at least 12 percent less than and thus superior to that of EXAMPLE 17 In accordancewith this example, 3-dimethylamino- N,N-dimethylpropionamide (AmineCatalyst 1) was combination with bis[2-(N,N- dimethylamino)ethy1]etheras the amine catalysts of a free-rise, high-resilience foam formulationcontaining tris(2,3-dibromopropy1)phosphate as an added flamehigher thanthat of the control formulation containing 0.80 p.p.h.p. ofN-ethylmorpholine.

EXAMPLES 13-16 In accordance with these examples, molded foams wereprepared employing Amine Catalysts Il-V, respectively, as directreplacements for N- ethylmorpholine (Control Run K-2) in ahigh-resilience foam formulation, designated herein as Foam FormulationB. The composition of this reaction mixture is given in the followingTable IV. 15 data are given in Table V.

I TABLE IV FOAM FORMULATION B Parts By Weight Control Examples '20Component K-2 13-16 Polyol A /1/ A 60 60 Polyol B /l/ 40 40Polysiocyanate A /1/ 34.38 34.38 Water 2.80 2.80

Ami SIS the control foam.

Amine Catalyst A /1/ 0.08 0.08 Amine Catalyst 8 /l/ 0.30 0.30N-Ethylmorpholine 0.80 None Amine Catalysts ll-V, respectively. None0.15 Dibutyltin dilaurate 0.03 0.03

Surfactant c 2 L50 L00 employed m /l/ Same as in Foam Formulation A ofTable 11. /2/ A polysiloxane oil having the average composition.

Me,Sio(Me Si0),[Me0(C H O) C H SiMeOI SiMe where Me is methyl, employedas a 10 weight percent solution in Polyol A.

High-Resilience Foam (Molded! xam le No.

retarding agent. A control foam was also prepared (Control R urrK -3)employing the same formulation ex- TABLE V Control Run No. K-2 Foam \lo.K-2 3 4 5 6 Foam Formulation B N-Ethylmorpholine, p.p.h.p. 0.80 NoneNone None None Amine Catalyst 11 /1/, p.p.h.p None 0.15 Amine Catalyst111 /2 p.p.h.p None 0.15 Amine Catalyst 1V /3/, p.p.h p None 0.15 AmineCatalyst V /4/, p.p.h.p None 0.15

Exit Time, seconds 47 48 46 49 Pop Time, seconds 107 114 I25 112 109 HotFoam Odor High Low Low Low Low Foam Properties Basal cell structure GoodGood Good Good Good Resilience, ball rebound 63 61 64 63 Porosity,t't.3lmin.lft. 21.5 39.5 26.5 32.0 21.5 Density, lbs/ft. 2.69 2.64 2.652.72 2.77 1LD(2-% 1bs./50in.

25% deflection 35.5 36.0 34.9 35.4 35.0 65% deflection 93.2 95.7 92.394.9 92.6 25% return 28.6 29.0 28.2 28.6 28.1 Return value, 80.6 80.580.8 80.8 80.3 Load Ratio 2.63 2.66 2.65 2.68 2.65 Compression Sets,

111 10.4 10.4 11.1 11.4 50% After Humid Aging /5/ 21 5 20.6 19.1 21.021.6 Tensile strength, psi. 26.5 26.5 28.2 29.0 26.2 Elongation, 172 177193 186 176 Tear Resistance, lbs/in. 2.34 2.38 2.46 2.38 2.44 Humid AgeLoad Loss, [5/ 30.7 26.9 26.5 23.9 24.8

cept that a 33 weight per cent solution of triethylenediamine wasemployed as the sole amine catalyst. The composition of the respectivereaction mixtures (Foam Formulation C) is given in Table V1. The foam ofthis EXAMPLES 18 and 19 7 In accordance with these examples, 3-(N-morphollno)-N,N-dimethylpropionamide and N,N'- piperazino-bis[3-(N",N"-dimethylpropionamide)],

example and the control foam were prepared following 5 designated hereinas Amine Catalysts V1 and V11, were freerise Foam Procedure 11. Theresults and foam physemployed as the respective sole amine catalysts ofa reical property data are also given in Table V1. action mixture (FoamFormulation D) which otherwise TABLE V1 HlGH-RESlLlENCE FOAM (Free-Rise)Example No. 17 Control Run No. K-3 Foam Io. K-3 7 Foam Formulation CParts by Weight Polyol B /l/ 50 50 Polyol Q: An ethylene oxide-capped,glycerol 50 50 started poly(oxypropylene) triol havinga Hydroxyl No. ofabout 27, a molecular weight of about 6000, and a primary hydroxylcontent of 80-85 mole per cent. Polyisocyanate B: A mixture of the 2,4-and 2.6- 28.3 28.3

isomers of tolylene diisocyanate, the weight ratio of said isomers being80:20. respectively. (Index 1 10) Diethanolamine 0.8 0.8 Water 2.0 2.0Amine Catalysts Amine Catalyst B: A 33 weight per cent solution 0.40None of triethylenediamine in dipropylene glycol. Bis[2-(N,N-dimethylamino)ethyllether (undiluted) None 0.06 Amine Catalyst 1/2/ None 0.24 Stannous octoate 0.06 0.06Tris(2,3-dibromopropyl)phosphatc 2.0 2.0 Surfactant C /3/ 1.0 10

Cream Time seconds 6 6 Rise Time seconds 155 185 Foam PropertiesResiliency, ball rebound 62 61 Porosity, ft."/min.lft. 37 40 Density.lbs/ft: 2.98 2.96 1LD(4"),1bs./50 in.

25% deflection 35.2 34.3 65% deflection 79.3 77.2 25% return 28.8 27.0Return value, 81.8 78.8 Load Ratio 2.25 2.25 Compression Sets, 7:

75% 5.7 6.1 7.2 7.5 Tensile strength, p.s.i. 21.1 20.6 Elongation, 187177 Tear Resistance, 1bs./in. 2.71 3.05 Humid Age Load Loss, [4/ 35.634.5 50% Compression Set After Humid Aging, 7c [4/ 11.9 13.4

/l/ As defined in Table n, V

/2/ 3-Dimethylamino-N.N-dimethylpropionamide. IJ/ As identified in TableIV.

'14! Aged five hours at 120C. in 100% relative humidity. v I I Theresults of Table V1 indicate thatFoam No. 7 and contains componentsemployed commercially for the Control Foam K-3 had excellent resiliencyand about 50 manufacture of free=rise (slabstock) flexible polyurethesame overall combination of physical properties. thane foam. The foamswere prepared following Foam Both foams were also of fine cellstructure. Although Procedure 11. The composition of Foam Formulation Du t o e y, as reflected y rise time,v was andthe results are given inTable VII which follows: higher in the case of the control reactionmixture, reactivity of the reaction mixture employed in Example 17 TABLEV11 was good. The higher reactivity observed for triethylenediamine isoffset by a number of advantages offered Emma: 18 19 by use of3-dimethylamino-N,N-dimethylpropionamide ML 8 9 Foam Formulation D PartsBy Weight in combination with b1s[2-(N,N-d1methylam1no)- Pol 0| Aglycembsmmd polymw m0 100 ethyl]ether. One such advantage 18 that thelatter cam propylene) triol having a Hydroxyl No.

' of about 56. lysts are both normally liquid materials whereas trleth MM am B: A mixture of the 49'75 4975 ylenediamme, although an excellentcatalyst, has the w 2764mm ofmmenc diiso.

processing disadvantage of being a solid. Perhaps more cyanate P n in aweight ratio of d h :20, respectively. (Index significantly,triethylenedlamine 18 also associate wit WM 4 4 a relatively strongamine odor which was noticeable as 65 Stannous octoate 0175 0.30 aresidual odor in the freshly prepared control foam. f g i 1/ 1 Q Q8 2 ISI On the other hand, freshly prepared Foam No. 7 was Amine Catalyst VIM0 completely free of any amine odor. Amine Catalyst VII 3/ 0.40

/1/ A polyoxyalkylene-polysiloxane block copolymer having the averagecomposition:

1( z)6.4( 2 +)|s( a s)u q nla wherein Me is methyl. /2/3'(N-Morpholino)-N',N'-dimethylpropionamide. /3/N,N'-Piperazino-bis[3'(N",N"dimethylpropionamide)]. /4/ Five hours at120C. in 100% relative humidity.

The data of Table VII demonstrate that Amine Catalysts V1 and VII arecatalytically active in promoting the isocyanate-water reaction, asreflected by rise time and the highly porous nature of the foamproducts. The

data also indicate the efficacy of these catalysts in allowing for theformation of flexible foams having a good combination of physicalproperties including low compression set values and low load lossesafter humid aging. These foams were also completely odorless.

EXAMPLES 20-23 In accordance with these examples, 3-dimethylamino-N,N-dimethylpropionamide (Amine Catalyst 1) and2-(N,N-dimethylam ino)ethyl 3-dimethylaminopropionate (Amine Catalyst X)were employed as the respective sole amine catalysts of Foam FormulationD (Table VII) in place of Amine Catalysts VI and VII. The foams wereprepared following freerise Foam Procedure 11. The concentration ofamine catalyst and stannous octoate employed in these examples and theresults are given in Table VIII which follows.

TABLE Vlll FLEXIBLE FOAMS (Free-Rise) Example No. 20 21 22 23 Foam No.10 11 12 13 Foam Formulation D [1/ Stannous octoate, p.p.h.p. 0.3 0.4250.25 0.275 Amine Catalyst 1 /2/, p.p.h.p. 0.1 0.20 Amine Catalyst X /3/,p.p.h.p. 0.40 0.20

Qream Time, seconds 11 1 1 12 13 Rise lime, seconds 90 70 100 103 FoamProperties Resiliency, ball rebound 45 44 45 46 Porosity, ft.=/min./t"t.97 61 93 93.5 Density, lbs/ft. 1.62 1.55 1.56 1.62 ILD (4"),1bs./50 in.

25% deflection 38.5 38.5 33.0 40.9 65% deflection 70 65.8 58.4 76.1 25%return 26.7 26.4 21.4 26.2 Return value, 69.4 68.6 64.9 64.0 Load Ratio1.82 1.71 1.77 1.86 Compression Sets.

Tensile strength, psi.

Table V111 Con tinued Elongation, 204 232 215 173 Tear Resistance,lbs./in. 2.63 2.72 2.43 2.07 Humid Age Load Loss, /4/ 6.8 8.17 9.18'14.7

ll/ ExCept for the variation in stannous octoate concentration and theamine catalyst employed, the composition of this formulation is asdefined in Table V11.

[2! 3-Dimethylami no-N,N-dimethylpropionnmide. l3/2(N.N-dimethylamino)ethyl 3-dimethylaminopropionnte. l4] Aged five hoursat 120C. in 100% relative humidity.

The results of Table VIII further indicate that the catalysts describedherein'are effective promoters of the water-isocyanate reaction and, asreflected by the relatively short rise time, Amine Catalyst 1 hasparticularly good reactivity in this respect. The data also indicatethat the flexible foam products were highly porous and had a goodoverall combination of properties. For the purpose of comparison, it isnoted that when 0.1 p.p.h.p. ofa weight per cent solution of bis[2-(N,N-dimethylamino)ethyllether (i.e.., Amine Catalyst A) is employed as thesole amine catalyst of Foam Formulation D at the same stannous octoatelevel (0.30 p.p.h.p.) employed in Example 20, the resulting formulationprovides a cream time of 10 seconds and a rise time of seconds, and theflexible foam product has the following properties (expressed on thebasis of the same units shown in Table VIII): porosity 58.7; resiliency46; density =1.45; 25% ILD 39.1; load ratio 1.72; percent compressionset 3.36; tensile strength 17.4; elongation 235; and humid age load loss14.1.

EXAMPLES 24-30 FOAM FORMULATION E Parts By Weight Control ExamplesComponent K-4 -24-30 figlygl E: A polyether triol having a 100l-Iydroxyl No. of 46 and containing less than 5 mole per cent of primaryhydroxyl groups, derived from glycerol, propylene oxide and ethyleneoxide, about 14 weight per cent of total oxide being ethylene oxide.

Pglyi ogyagatg B: An 80:20 mixture of 48.2 48.2

the 2,4- and 2,6- isomers of tolylene diisocyanate, respectively.(lndex=) Water 4.0 4 0 Stannous octoate 0.25 0 25 Surfactant D /l/ 1.0 l0 in a s i A 70 weight per cent 0.1 solution ofbisl2-(N,N-dimethylamino)- ethyllether in dipropylene glycol.

MA 67/33 parts by weight blend 0.1

of Amine Catalysts l-V, Vlll or IX andbis[2-(N.N-dimethylamino)ethyllether. I

/1/ As defined in Table VI].

' were Foam Nos. 15-18 based on Amine Catalysts Il-V,

' As indicated in Table IX, the catalysts employed in the examples wereadded as blends (01 part) containing 67 and 33 parts by weight of thebeta-amino carbonyl compound and bisether, respectively, therebycatalysts associated with the odor characteristic of amines, freshlyprepared Foams 14-20 were odorless.

EXAMPLES 31-37 [ethyl 3-(N,N-diethylamino')propionate]. In additiontotheir enhanced porosity, Foam Nos. 14-20 also err; hibited lower loadlossvalues afterhumid aging than thecontrol foam; especially outstandingin this respect respectively. Of furthersignificance is the realizationof these improvements without the necessity of employing providing 0.067and 0.033 part by weight of each type of catalyst per 100 parts ofpolyol reactant (p.p.h.p.). In accordance with these examples, anotherseries of As further indicated in Table IX, the control formulafoams wasprepared employing respective reaction tion employed in Control Run K-4,contained the bisetmixtures based on the blends of Amine Catalysts IV,her (0.070 p.p.h.p.) as the sole amine catalyst, added VIII and IXdescribed under Examples 24-30. The as 0.1 part of a 70 weight per centsolution thereof. The 10 composition of the reaction mixtures (FoamFormulavarious foams were prepared following Foam Procetion F) includingthat employed in ControI'Run K-5 is dure II. The results are given inTable X. t given in Table XI.

TABLE X Example No. 24 2'5 26 27 28 29 30 Control Run No. K-4 Foam No.K-4 14 15 16 17 18 19 20 w l I Amine Catalyst No. 1 11 111 IV v v111 1xParts b Weight p.h.p. None 0.067 0.067 0.067 0.067 0.067 0.067 t 0.067Bisl2-(N.N-dimethylamino)ethyl]ether, p.p.h.p. 0.070 0.033 0.033 0.0330.033 0.033 0.033 0.033

Qream Time, seconds 9 l0 9 l0 1 9 9 9 I II Rise Time, seconds 78 94 8280 78 78 90 90 Foam Properties Resiliency, ball rebound 44 42 44 47 4342 42 Porosity, rtfivminlrt. 55.5 107.5 --73.6 75.8 73.6 75.8 90.4 97.4Density, 1bt./rt. 1.53 1. 0 1.61 1.56 1.59 1.62 1.63 1.66 11.1) (4"Ibs./50 in.

25% deflection 39.1 38.6 37.8 38.4 36.2 36.0 42.8 41.7 deflection 66.066.8 9.9 69.5 66.9 67.4 73.2 73.4 25% return 247 24.6 24.5 24.1. 24.023.9 26.3 25.8 Return value, 63.2 63.7 64.8 63.5 66.3 66.4 61.4 61.9Load Ratio 1.69 1.73 1.85 1.81 1.84 1.87 1.71 1.76 Compression Sets,

I 5.50 5.51 7.33 7.14 8.13 6.95 4.66 5.12 50% After Humid Aging /2/ 6.236.56 11.1 10.6 11.8 11.3 6.02 5.94 Tensile strength, p.s.i. 20.0 17.418.3 I8.5 I9.4 l9.l l7.20 l7.I Elongation,% 273 248 279 292 290 284- 23324s Tear Resistance, lbsJin. 3.14 3.02 4.20 3.58 3.6l 3.60 3.47 3.02Humid Aged Load Loss, /2/ 24.8 20.2 16.6 14.8 14.5 15.8 l8.7 18.5

[H As defined in Table IX. I2! After aging for five hours at 120C. inl00% relative humidity.

The results of Table X indicate that the blended BLE I-.. aminecatalysts employed in Examples24-30 provided flexible foams having anoverall good combination of FOAM FORMULATION F Pa ts By w m r ergphys1cal propert1es as compared with Control Foam. 5 Control Examples L4 Component |(.5 3 7 K-4 and that certaln indivtdual propert1es weresupe- I .Pol 0| E /1/. 100 Thus In each Instance, F .7 werePolzisocyanate a /l/(Index= 37.9 37.9 markedly more porous than thecontrol foam; particu- 9 Stannous octoate 0.275 0.275 larly outstandmgin this respect were Foam No. 14 50 SurfactantE/Z/ 1.0 1.0 basedv onAmine Catalyst I (3-dimethylamino N,N- 5min: Q t I vdimethylpropionamide), Foam No. 19 based on Amine MM 70 Weigh! W "01!cent solution of b1s[2-(N,N- Catalyst VIII [ethyl.3-(N,N-d1methylammo)prop1on-; gime hy n t y l in ipwpyenegyco ate], andFoam No. 20 based on Am ne Catalyst IX 55 MA 67/33 parts by weight blend0.1

of Amine Catalysts I-V, VIII or IX and his [2-(N,N-dimethylamino)ethyl1-ether.

ll/ As defined in Table IX.

A polysiloxane-polyoxyalkylene average composition MeSiO(MeeSiO)1e[MeO(C I-IiO) oC H SiMeOhSiMe where Me is methyl, employedas a 55 weight percent active solution. H H

blocle copolymer having the

2. The method of claim 1 in which said alkyl beta-(dialkylamino)carboxylate is ethyl 3-(N,N-dimethylamino)propionate.
 3. A methodfor producing a urethane polymer which comprises reacting an organicpolyisocyanate and an organic polyol having an average of at least twohydroxyl groups per molecule, in the presence of a2-(N,N-dialkylamino)ethyl 3-(N'', N'' -dialkylamino)carboxylate havingthe formula:
 4. The method of claim 3 in which said2-(N,N-dialkylamino)ethyl 3-(N'', N''-dialkylamino)carboxylate is2-(N,N-dimethylamino)ethyl 3-(N'',N''-dimethlamino)propionate.
 5. Amethod for producing a polyurethane foam which comprises reacting anorganic polyisocyanate and an organic polyol reactant comprising apolyether polyol having an average of at least two hydroxyl groups permolecule, in the presence of a blowing agent and a catalyst comprising a3-dialkylamino-N,N-dimethylamide having the formula:
 6. The method ofclaim 5 in which said 3-dialkylamino-N,N-dimethylamide is3-dimethylamino-N,N-dimethylpropionamide.
 7. The method of claim 5 inwhich the lower alkyl groups represented by R1 and R2 of said3-dialkylamino-N,N-dimethylamide are other than methyl.
 8. The method ofclaim 5 in which R3 of said 3-dialkylamino-N,N-dimethylamide is a loweralkyl group.
 9. A method for producing a urethane polymer whichcomprises reacting an organic polyisocyanate and an organic polyolhaving an average of at least two hydroxyl groups per molecule, in thepresence of a beta-amino carbonyl compound having the formula,
 10. Aprocess for producing flexible polyurethane foam which comprisessimultaneously reacting and foaming a reaction mixture containing: (a)an organic polyisocyanate; (b) an organic polyol reactant comprising apolyether polyol having an average hydroxyl functionality of from 2.1 toabout 4 and a hydroxyl number from about 20 to about 100; (c) water as asource of blowing action; and (d) an amine catalyst comprising a3-dialkylamino-N,N-dimethylamide having the formula,
 11. The method ofclaim 10 in which said organic polyol comprises a mixture of saidpolyether polyol and a polymer/polyol produced by the in situpolymerization of at least one polymerizable ethylenically unsaturatedmonomer in a polyether polyol.
 12. The method of claim 10 in which theisocyanato groups of said organic polyisocyanate are bonded to anaromatic nucleus.
 13. The method of claim 12 in which said organicpolyisocyanate is a tolylene diisocyanate.
 14. The method of claim 12 inwhich said organic polyisocyanate is a polyphenylmethylenepolyisocyanate.
 15. The method of claim 10 in which said organicpolyisocyanate is a mixture of isomeric tolylene diisocyanates andpolyphenylmethylene polyisocyanates.
 16. The method of claim 10 in whichsaid reaction mixture additionally contains a tertiary amine catalystconsisting of carbon, hydrogen and nitrogen and having no more than 12carbon atoms.
 17. The method of claim 16 in which said additionaltertiary amine catalyst is triethylene-diamine.
 18. The method of claim16 in which said additional tertiary amine catalyst isN,N,N'',N''-tetramethyl-1,3-butanediamine.
 19. The method of claim 10 inwhich said reaction mixture additionally contains a tertiary aminecatalyst consisting of carbon, hydrogen, nitrogen and oxygen whereinsaid oxygen is present as an ether oxygen or a hydroxyl group, saidadditional catalyst having no more than 12 carbon atoms.
 20. The methodof claim 19 in which said additional tertiary amine catalyst is abis(2-(N,N-dimethylamino)alkyl)ether.
 21. The method of claim 19 inwhich said additional tertiary amine catalyst is an N-alkylmorpholine.22. The method of claim 10 in which said amine catalyst componet (d)additionally includes a tertiary amine selected from the groupconsisting of triethylene-diamine, bis(2-(N,N-dimethylamino)ethyl)etherand mixtures thereof.
 23. The method of claim 10 in which said reactionmixture additionally contains an organic derivative of tin selected fromat least one of the group consisting of stannous salts of carboxylicacids and dialkyltin dicarboxylates.
 24. The method of claim 10 in whichsaid 3-dialkylamino-N,N-dimethylamide is added to the reaction mixtureas a solution in a butanol-started polyoxyethylene-polyoxypropylenefluid.
 25. The method of claim 10 in which said3-dialkylamino-N,N-dimethylamide is added to the reaction mixture incombination with an organic non ionic surfactant.
 26. The method ofclaim 25 in which said non ionic surfactant is an ethylene oxide adductof nonylphenol.
 27. The method of claim 10 in which said reactionmixture additionally contains a flame-retardant.
 28. A flexiblepolyurethane foam produced in accordance with the method of claim 10.29. A method for producing a high resilience polyurethane foam whichcomprises reacting and foaming a reaction mixture containing: (a) anorganic polyisocyanate reactant wherein the isocyanato groups are bondedto aromatic nuclei; (b) a polyether polyol having an averagefunctionality of about 3, a hydroxyl number from about 21 to about 84and a primary hydroxyl content from about 60 to about 90 mole per cent;(c) a polymer/polyol produced by the in situ polymerization of at leastone polymerizable ethylenically unsaturated monomer in a polyetherpolyol; (d) water as a source of blowing action; and (e) a catalyticamount of a 3-dialkylamino-N,N-dimethylamide having the formula,
 30. Themethod of claim 29 in which said polymer/polyol is a reaction productproduced by polymerizing at least one monomer of the class consisting ofstyrene, alpha-methylstyrene, acrylonitrile and methacrylonitrile, in apolyether polyol having an average hydroxyl functionality from about 2.1to about
 4. 31. The method of claim 29 in which said polyether polyolcomponent (b) and the polyol in which said polymer/polyol component (c)is polymerized, are glycerol-started polyoxypropylene ethers wherein thepolyoxypropylene chains are capped with ethylene oxide.
 32. The methodof claim 29 in which a dialkyltin dicarboxylate is present as anadditonal component of the reaction mixture.
 33. The method of claim 29in which said 3-dialkylamino-N,N-dimethylamide is3-dimethylamino-N,N-dimethylpropionamide.
 34. The method of claim 29 inwhich said reaction mixture contains bis(2-(N,N-dimethylamino)-ethyl)ether as an additonal catalytic Component thereof.
 35. A high-resiliencepolyurethane foam produced as a product of the process of claim
 19. 36.The method of claim 1 in which said alkyl beta-(dialkylamino)carboxylateis ethyl 3-(N,N-diethylamino)propionate.
 37. The method of claim 9 inwhich said beta-amino carbonyl compound isN,N''-piperazino-bis(3-(N'''',N''''-dimethylpropionamide)) .
 38. Themethod of claim 7 in which said 3-dialkylamino-N,N-dimethylamide is3-diethylamino-N,N-dimethylpropionamide.
 39. The method of claim 8 inwhich said 3-dialkylamino-N,N-dimethylamide is3-dimethylamino-N,N-dimethylbutyramide.
 40. A method for producing ahigh resilience polyurethane foam which comprises reacting and foaming areaction mixture containing: (a) an organic polyisocyanate comprising atolylene diisocyanate; (b) a polyether triol having an average primaryhydroxyl content of at least 40 mole per cent and an average molecularweight from about 2,000 to about 8,000; (c) a polymer/polyol prepared bythe in situ polymerization of a monomer mixture containing from about 50to about 75 weight per cent of acrylonitrile and from about 50 to about25 weight per cent of styrene in a polyether triol having an averageprimary hydroxyl content of at least 40 mole per cent and an averagemolecular weight from about 2,000 to about 8,000; (d) water as a sourceof blowing action; (e) 3-dimethylamino-N,N-dimethylpropionamide and (f)at least one additional tertiary amine selected from the groupconsisting of triethylenediamine andbis(2-(N,N-dimethylamino)ethyl)ether, said components (e) and (f) beingpresent in said reaction mixture in respective amounts between about0.01 and about 5 parts by weight per 100 parts by weight of totalpolyols (b) and (c) contained in the reaction mixture.